TW201545877A - Multilayer product - Google Patents

Abstract

The present invention relates to a multilayer product comprising at least one layer of an acrylate-based foam carrier (S); and a multiphase polymer composition (P) applied to this layer; the multiphase polymer composition (P) comprising: ○ a comb copolymer (A) which is obtainable by polymerization of at least one (meth)acrylate monomer in the presence of at least one macromer selected from the group consisting of polymerizable ethylene-butylene, ethylene-propylene, ethylene-butylene-propylene and isobutylene macromers, and which forms a continuous acrylate phase and a discontinuous hydrocarbon phase Kw; ○ and at least one hydrocarbon component (B) which is soluble in the hydrocarbon phase Kw of the comb copolymer (A) and comprises at least one plasticizer resin and at least one solid resin; the multiphase polymer composition (P) having a continuous acrylate phase with a static glass transition temperature Tg(Ac), measured by the DSC method, and a discontinuous hydrocarbon phase Kw1, comprising the hydrocarbon component (B) and having a staticglass transition temperature Tg(Kw1), measured by the DSC method, where Tg(Kw1) is higher than Tg(Ac) by 35 to 60 kelvins, preferably by 40 to 60 kelvins, more preferably by 45 to 60 kelvins. The invention relates further to a method for producing the multilayer product, to an adhesive tape comprising the multilayer product, and to the use of the multilayer product for adhesive bonding of articles.

Description

Multilayer product

The present invention relates to a multilayer article comprising a foam carrier (S) comprising at least one acrylate substrate; and a heterophasic polymer composition (P) applied to the layer. The heterophasic polymer composition comprises a comb copolymer (A) which forms a continuous acrylate phase and a discontinuous hydrocarbon phase; and also at least one hydrocarbon component (B) which is soluble in the The comb copolymer is in the hydrocarbon phase (A). The invention further relates to a tape comprising the multilayer article of the invention; and also to the use of the multilayer article for gluing bonding of articles, more particularly for gluing bonding of articles having non-polar surfaces. A method for making a multilayer article is also described.

Pressure sensitive adhesive products of acrylate substrates are known from the prior art. Its chemical resistance makes the adhesive of acrylate substrates particularly suitable for bonding in industrial applications. However, this known composition has the disadvantage that it is difficult to use on a substrate having a low surface energy ("low surface energy" material, hereinafter referred to as LSE material). This difficulty is manifested on the one hand in the adhesion strength of the known pressure sensitive adhesives (PSAs) on non-polar substrates such as polypropylene or steel such as LSE varnish coated; and, as such, on the other hand, Its maximum bond strength is at the speed. Known acrylate substrate PSAs are the mainstay of low adhesion strength on non-polar surfaces The reason for this is considered to be the difference in surface energy between the known polymer composition and the LSE material, and the lack of attachment points suitable for covalent or strong non-covalent bonding within the LSE surface. Furthermore, the adhesion between the polymer composition of the known acrylate substrate and the surface of the LSE is essentially based on a rather weak Van der Waals force.

One method of developing a higher bond strength between the LSE surface and a polyacrylate based polymer composition is to use a tackifying resin. Another method is to use a primer, i.e., an adhesion promoter, to increase the surface energy of the LSE substrate. While the use of a primer is generally expensive and inconvenient, the use of a tackifying resin results in a decrease in the cohesive force of the polymer composition, which in turn may cause the bond to break under load. This loss of cohesion is particularly critical when the polymer composition in question is used for bonding to a particular force such as, for example, a vibrating object. The corresponding vibrations are observed on the components of the automotive sector, in particular in the region of the vehicle body or in the engine compartment.

In areas where tape is required to be temporarily or permanently attached to paints and varnishes, especially in the automotive sector, many new developments have created a desired bond strength even on non-polar surfaces without the need for approval. There is any compromised tape on cohesion. Furthermore, this PSA should have good chemical resistance and develop high adhesion strength only after a short time. Furthermore, given the increased demand for low fuel consumption in the automotive sector, the tape supplied to this PSA should have a low weight. In order to reduce the volumetric weight of the tape, a foam carrier of an acrylate substrate has been proposed in the past.

An embodiment of a tape comprising a foam carrier of this type of acrylate substrate is described in EP 2 226 369 A1. However, the tape described therein contains a PSA based on a chemically crosslinked rubber, and thus resistance to a chemical such as, for example, petroleum spirit cannot be properly ensured.

Although an adhesive using an acrylate substrate will increase the chemical resistance as compared with an adhesive for a rubber substrate, simply converting the rubber PSA into a PSA of an acrylate substrate has the possibility of carrying the above problems on the LSE material. However, due to the above vibrations, particularly in the automotive sector, it is not appropriate to use a tackifying resin to improve the bonding strength of the PSAs of the acrylate substrate. Furthermore, over time, the tackifying resin used may drift from the PSA into the foam carrier layer of the acrylate substrate, which will result in additional loss of bond strength over time. Another method known from the prior art, i.e. the use of a primer, is equally impossible for reasons that can be carried out on the surface area of a motor vehicle.

In this context, there is a basic need for multilayer articles that do not accept any cohesive force compromise requirements and have good bond strength on non-polar surfaces. Multilayer articles should further have good chemical resistance, develop high bond strength only after a short period of time, have low weight and retain high bond strength for a long period of time.

Invention goal

Moreover, the present invention is based on the object of providing an improved multilayer article.

Introduction to the invention

The present invention solves this object and the problems of the prior art by providing a multilayer article comprising: - at least one layer of acrylate base foam carrier (S); and - a heterophasic polymer composition applied to the layer (P) The heterophasic polymer composition (P) comprises: o a comb-shaped copolymer (A) which can be obtained by at least one selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butene - obtaining at least one (meth) acrylate monomer in the presence of a macromonomer composed of a group of propylene and isobutylene macromonomers, and forming a continuous acrylate phase and a discontinuous hydrocarbon phase Kw; ○ and at least one hydrocarbon component (B) which is soluble in the hydrocarbon phase (A) of the comb copolymer and comprises at least one plasticizer resin and at least one solid resin; the heterophasic polymer composition The substance (P) has a continuous acrylate phase having a static glass transition temperature Tg(Ac) as measured by the DSC method; and a discontinuous hydrocarbon phase Kw1 comprising the hydrocarbon component (B) And having a static glass transition temperature Tg (Kw1), which is measured by the DSC method; wherein T g(Kw1) is 35 to 60 grams of errone, preferably 40 to 60 grams of oturology, more preferably 45 to 60 grams of otography, above Tg (Ac).

The static glass transition temperature Tg (Kw1) of the discontinuous hydrocarbon phase in the polymer composition (P) is preferably in the range of -5 to +15 °C, more preferably 0 to +10 °C. The static glass transition temperature Tg(Ac) of the continuous acrylate phase in the polymer composition (P) is preferably less than -10 ° C, more preferably in the range of -60 to -20 ° C, very preferably The range is -50 to -30 °C.

The invention further relates to a method for making a multilayer article, the steps comprising: (i) providing a foam carrier (S) layer having an upper and a bottom acrylate substrate; and (ii) the foam Applying a heterophasic polymer composition (P) to the upper side and/or the bottom side of the carrier (S); the heterophasic polymer composition (P) comprises: ○ a comb copolymer (A) which can be at least Polymerization of at least one (meth) acrylate in the presence of a macromonomer selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butylene-propylene, and isobutylene macromonomers Obtained as a monomer, and forms a continuous acrylate phase with a discontinuous hydrocarbon phase Kw; ○ and at least one hydrocarbon component (B) which is soluble in the hydrocarbon phase of the comb copolymer (A) And comprising at least one plasticizer resin and at least one solid resin; the heterophasic polymer composition (P) having a continuous acrylate phase having a static glass transition temperature Tg(Ac) by DSC method Measuring; and a discontinuous hydrocarbon phase Kw1 comprising the hydrocarbon component (B) and having a static glass transition temperature T g(Kw1), which is measured by the DSC method; wherein Tg(Kw1) is 35 to 60 gram er, higher than Tg(Ac), preferably 40 to 60 gram, and more preferably 45 to 60. Kelvin.

Once the multiple polymer chains of the respective comb copolymer molecules are in contact with each other, the heterophasic polymer composition (P) is applied to the comb copolymer (A) described herein such as, for example, after removing the solvent. A continuous acrylate phase is formed with a discontinuous hydrocarbon phase. Here, in the acrylate The combination of the backbone with the hydrocarbon side chains produces a continuous acrylate phase and a discontinuous hydrocarbon phase.

The heterophasic polymer composition (P) has at least two phases: at least one hydrocarbon phase and one acrylate phase. The presence of these phases is evidenced by the static glass transition temperature of the polymer composition as determined by DSC. In addition or in addition, the presence of different phases can be confirmed by dynamic mechanical analysis (DMA) in accordance with ASTM D4065-12. Here, in the temperature sweep measurement, two or more glass transitions caused by the respective constituents of the composition are measured.

The continuous acrylate phase of the polymer composition (P) has a static glass transition temperature Tg (Ac), which is measured by the DSC method (measurement method A-4). The discontinuous hydrocarbon phase Kw1 has a static glass transition temperature Tg (Kw1) which is measured by the DSC method (measurement method A-4). The static glass transition temperature Tg(Kw) of the polymer composition differs from Tg(Ac) by 35 to 60 gram, preferably 40 to 60 gram, more preferably 45 to 60 gram, where Tg ( Kw1) is greater than Tg(Ac).

Due to the special combination of the comb copolymer (A) and the hydrocarbon component (B) soluble in the hydrocarbon phase Kw of the comb copolymer (A), the composition is stable but different in phase, in other words , without macroscopic phase separation into a comb copolymer (A) on the one hand and a hydrocarbon component (B) on the other hand.

The heterophasic polymer composition (P) has proven to be particularly suitable for gluing bonding of articles having LSE surfaces. Furthermore, it has chemical resistance and UV stability, and has high cohesion at room temperature (25 ° C) and high temperature, and is characterized by high shear strength. Surprisingly, however, the polymer composition (P) ensures rapid flow onto the surface of low energy objects. And coating the surface of LSE varnish, and also other LSE materials, and allowing high bond strength to develop in a short time. The heterophasic polymer composition (P) further allows for the supply of a transparent PSA layer.

Moreover, in a further aspect, the present invention is directed to an adhesive tape comprising the multilayer article described herein. Therefore, a multilayer article that supplies a tie tape is also described. The polymer composition (P) is preferably a PSA, more preferably a transparent PSA. It is further described that the multilayer article is used for gluing bonding of articles, and more particularly for gluing bonding of articles having low surface energy (LSE materials). For the purposes of the present invention, this LSE material includes a material that is not actually a LSE material, but whose surface is associated with an adhesive as a LSE material due to a coating, such as a material having a LSE varnish coating.

1‧‧‧First assembly

2‧‧‧Second assembly

3‧‧‧ third assembly

4‧‧‧ Roll calender

5‧‧‧Mold

11,37b‧‧‧Connected section

11,24b‧‧‧heatable hose

22,23,34,35,36‧‧‧measuring points

24‧‧‧Second connection

24a, 37a‧‧‧melting pump

31,32‧‧‧ mixed area

33,34,35‧‧‧Measuring equipment

36‧‧‧Sliding seal ring

37‧‧‧Transportation unit

41,42,43‧‧‧roll

44‧‧‧Carrier materials

B‧‧‧ blister

S, T ₁ , T ₂ , T ₃ , T ₄ ‧ ‧ section

V‧‧‧vacuum dome

The method is set forth in more detail below with reference to the two figures, without any intention, and the teachings in accordance with the present invention should not necessarily be limited by this exemplary representation. In the figure: Figure 1 shows a particularly useful device architecture for performing the method; and Figure 2 is superimposed on a previously arranged device architecture, for example, showing the location assignment of the individual process steps, and additional In particular, temperature and pressure parameters.

Detailed description of the invention

According to the invention, the above object is achieved by a multilayer article comprising: a foam carrier carrier (S) of at least one acrylate base; and - a heterophasic polymer composition (P) applied to the layer; the heterophasic polymer composition (P) comprising: ○ a comb copolymer (A), which may be present in the presence of at least one macromonomer selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butylene-propylene, and isobutylene macromonomers, Obtained by polymerizing at least one (meth) acrylate monomer, and forming a continuous acrylate phase with a discontinuous hydrocarbon phase Kw; ○ and at least one hydrocarbon component (B), which is soluble in the comb a hydrocarbon phase Kw of the shaped copolymer (A) and comprising at least one plasticizer resin and at least one solid resin; the heterophasic polymer composition (P) having a continuous acrylate phase having a static glass transition temperature Tg(Ac), which is measured by the DSC method; and a discontinuous hydrocarbon phase Kw1 comprising the hydrocarbon component (B) and having a static glass transition temperature Tg (Kw1), which is measured by the DSC method Wherein Tg (Kw1) is 35 to 60 grams of erlang, preferably 40 to 60 grams of whis, more preferably 45 to 60 grams of ear, higher than Tg (Ac) .

In a preferred embodiment, the polymer composition described herein has the following characteristics, wherein the static glass transition temperature Tg (Kw1) of the discontinuous hydrocarbon phase within the polymer composition is in the range -5 to Within +15 ° C, preferably 0 to +10 ° C. Also preferably, the static glass transition temperature Tg(Ac) of the continuous acrylate phase in the polymer composition is less than -10 ° C, preferably in the range of -60 to -20 ° C, more preferably In the range of -50 to -30 °C.

A suitable polymer composition can be obtained by first providing a comb copolymer (A) whose polymer skeleton (hereinafter also referred to as "backbone", "polymer backbone" or "backbone") At least 20 weight percent of the acrylate monomer unit composition, based on the total weight of the polymer backbone, is preferably at least 50 weight percent, more preferably at least 80 to 100 weight percent. For this purpose, at least one, preferably at least two, more preferably at least three (meth) acrylate units, at least one selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, according to the invention Polymerization is carried out in the presence of a macromonomer of a group consisting of ethylene-butene-propylene and isobutylene macromonomers.

The at least one (meth) acrylate monomer used to prepare the comb copolymer (A) may be two or more, more preferably a monomer mixture of three or four (meth) acrylate monomers, And preferably comprising at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, methyl acrylate, butyl acrylate, acrylic acid Ester, stearyl acrylate, isostearyl acrylate, amyl acrylate, isooctyl acrylate, decyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and 4-hydroxybutyl acrylate; preferably selected from In the group consisting of acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, methyl acrylate, butyl acrylate, acrylic acid Ester, stearyl acrylate, isostearyl acrylate, amyl acrylate, isooctyl acrylate and decyl acrylate.

In a preferred embodiment of the invention, at least one (meth) acrylate monomer or a monomer mixture of two or more (meth) acrylate monomers of the comb copolymer is used (under "single The polymerization of the bulk mixture ") occurs in the presence of at least one further copolymerizable monomer. The further copolymerizable monomer is preferably selected from the group consisting of itaconic acid, itaconic anhydride, Maleic acid, maleic anhydride, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl isobutyrate, vinyl valerate, vinyl versatates, N-vinyl pyrrolidine Ketones and N-vinyl caprolactam.

It is also preferred that the polymerization of the at least one (meth) acrylate monomer or monomer mixture used to prepare the comb copolymer is carried out in the presence of a further second macromonomer. The additional second macromolecule single system is a non-polyolefin macromonomer, preferably selected from the group consisting of polymethacrylates, polystyrenes, polydimethyloxanes, and polyepoxys. Alkanes and polypropylene oxides.

In addition to the comb copolymer (A), the polymer composition (P) comprises at least one hydrocarbon component (B) soluble in a hydrocarbon phase of the comb copolymer, comprising at least one solid resin and At least one plasticizer resin. "Hydrocarbon component" means that the constituent of this component is a hydrocarbon. Both the solid resin and the plasticizer resin are preferably hydrocarbon resins having a number average molecular weight Mn of 1000 g/mole or less, as measured by the GPC method. In a particularly preferred embodiment, the hydrocarbon component (B) is composed of a solid resin (B-1) and a plasticizer resin (B-2).

In a further embodiment of the invention, the polymer composition (P) further comprises a hydrocarbon compound (C) having a number average molecular weight (Mn) of greater than 1000 g/mol, as measured by the GPC method. In a further embodiment, the polymer composition comprises at least one plasticizer selected from the group consisting of acrylate phases soluble in the comb copolymer (A), oil and The additive of the group consisting of resins is preferably a rosin ester and/or a terpene-phenol resin.

According to one aspect of the invention, the heterophasic polymer composition (P) can be prepared by a process comprising the steps of: - at least one selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene In the presence of a macromonomer of a group consisting of butene-propylene and isobutylene macromonomers, at least one, preferably at least two, more particularly at least three, for example three or four (methyl) groups are polymerized. An acrylate monomer to form a comb copolymer (A) having an acrylate backbone and a hydrocarbon side chain; - mixing the resulting comb copolymer (A) with at least one resin comprising at least one plasticizer and at least A hydrocarbon component (B) of a solid resin which is compatible with a hydrocarbon side chain of the comb copolymer (A); and, similarly, a selectively crosslinkable reactive functional group.

The composition of the polymer composition (P) is described in more detail below.

Comb copolymer (A)

Comb copolymers (or comb-shaped graft copolymers) are polymers having an architectural character in which the side chains they carry on their backbone (polymer backbone) are already considered polymers due to their length.

As used herein, the comb copolymer (A) is intended to symbolize, more particularly, by at least one selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butene-propylene and isobutylene. A copolymer obtained by radically polymerizing at least one (meth) acrylate monomer or monomer mixture in the presence of a macromonomer composed of a group of macromonomers.

(meth) acrylate monomer

The comb copolymer (A) of the polymer composition (P) can be polymerized by at least one (meth) acrylate monomer or two or more, for example, three or four, in the presence of at least one macromonomer. A monomer mixture of (meth) acrylate monomers is prepared. Further copolymerizable monomers may also participate in the polymerization. The at least one (meth) acrylate monomer or the monomer mixture comprising the at least one (meth) acrylate monomer preferably constitutes all of the constituents involved in the polymerization, ie, results in the comb copolymer (A) All of the constituents, that is, all of the copolymerizable monomers, macromonomers, including the at least one (meth) acrylate monomer, 50-99, more preferably 75-95, very preferably 85- 90 weight percent. The macromolecular system is preferably present in an amount of from 1 to 50, more preferably from 5 to 25, and most preferably from 10 to 15% by weight, to participate in all of the constituents which cause polymerization of the comb copolymer (A). The basis, that is, based on all copolymerizable monomers and macromonomers, including the at least one (meth) acrylate monomer.

The at least one (meth) acrylate monomer may be a monomer mixture of two or more, more preferably three or four (meth) acrylate monomers, and preferably at least one selected from the group consisting of Monomers of the following group: acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, methyl acrylate, butyl acrylate, acrylic acid Ester, stearyl acrylate, isostearyl acrylate, amyl acrylate, isooctyl acrylate, decyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and 4-hydroxybutyl acrylate; preferably at least one a monomer selected from the group consisting of acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, methyl acrylate, butyl acrylate, acrylic acid Ester, stearyl acrylate, isostearyl acrylate, amyl acrylate, isooctyl acrylate and decyl acrylate.

In a preferred embodiment of the invention, the at least one (meth) acrylate monomer or a monomer mixture of two or more (meth) acrylate monomers (hereinafter referred to as "monomer mixture") The polymerization is carried out in the presence of at least one further copolymerizable monomer. The further copolymerizable monomer is preferably selected from the group consisting of itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, vinyl acetate, vinyl butyrate, vinyl propionate, Vinyl isobutyrate, vinyl valerate, vinyl neodecanoate, N-vinylpyrrolidone and N-vinyl caprolactam.

As described herein, at least one (meth) acrylate monomer polymerizable to form the comb copolymer (A) by polymerization in the presence of at least one macromonomer is preferably selected such that The continuous acrylate phase of the heterophasic polymer composition of the invention has a static glass transition temperature Tg(Ac) of less than -10 ° C, preferably in the range of -60 ° C to -20 ° C, more preferably in the range of -50 To -30 ° C. For this purpose, it is preferred to use at least one, more preferably at least two monomers known as low Tg (meth) acrylate monomers, the homopolymer having a static glass transition temperature (Tg) of 40 ° C or Lower, this is measured by the DSC method (measurement method A4), preferably 25 ° C or lower. This type of "low Tg" single system is described in J. Brandrup, EH Immergut, EAGrulke, Polymer Handbook, 4th Edition, 1998. In a preferred embodiment, the at least one (meth) acrylate monomer comprises at least one (meth) acrylate monomer having a C ₁ -C ₁₈ alkyl group in the ester group, preferably butyl acrylate. Ester, amyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate and decyl acrylate.

The at least one (meth) acrylate monomer, or in the case of a mixture of two or more (meth) acrylate monomers, a monomer mixture comprising these (meth) acrylate monomers is therefore preferred. It is a low Tg monomer or a mixture of such monomers. Preferably, the low Tg monomer or mixture is present in a weight fraction of from 43 to 97 weight percent, based on all of the constituents that result in polymerization of the comb copolymer (A). In this preferred embodiment, the polymerization of the at least one (meth) acrylate monomer is advantageously carried out in the presence of acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride. And/or further so-called high Tg monomers whose homopolymers have a static glass transition temperature (Tg) higher than 40 ° C, which is measured by the DSC method (measurement method A4), preferably higher than 80 °C. This type of "high Tg" single system is described in J. Brandrup, E. H. Immergut, E. A. Grulke, Polymer Handbook, 4th Edition, 1998. Acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, and/or other high Tg monomers are preferably present in a amount of from 2 to 7, more preferably from 2 to 6 parts, very Preferably, it is a component of 3-5 weight percent based on the total weight of all monomers and macromonomers participating in the polymerization.

Therefore, in a preferred embodiment of the present invention, the comb copolymer (A) may be selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, and at least one of 2-7 weight percent. In the presence of a monomer of a group consisting of maleic acid and maleic anhydride, at least one (meth) acrylate monomer or two or more are polymerized based on the total weight of all constituents participating in the polymerization. These (meth)acrylate single system low Tg monomers are obtained from a monomer mixture of acrylate monomers.

In other words, in addition to the at least one macromonomer, the participant in the polymerization leading to the comb copolymer (A) is preferably at least three monomers, one of which is selected from the group consisting of: Acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride and its homopolymers have further monomers having a static glass transition temperature (Tg) higher than 40 ° C, which is by DSC The method measures, preferably above 80 ° C (also referred to herein as "high Tg" monomer). As used herein, the term "high Tg" single system is based on the static glass transition temperature of the homopolymer, as in J. Brandrup, EH Immergut, EAGrulke, Polymer Handbook, 4th Edition, 1998. Described. Therefore, the participation preferably results in the polymerization of the comb copolymer (A) (hereinafter also referred to as "polymerization") being only one of these high Tg comonomers, more preferably acrylic acid or methacrylic acid, more preferably For acrylic acid. According to the present invention, the amount of the high Tg comonomer is preferably from 2 to 7 weight percent based on the total weight of all the constituents participating in the polymerization, preferably from 2 to 6, more preferably from 3 to 3. 5 weight percent.

In one embodiment, the polymerization is carried out in the presence of up to 20% by weight of at least one further copolymerizable monomer, preferably up to 15 weight percent (based on the total weight of all constituents participating in the polymerization), Wherein the single system is selected from the group consisting of: acrylic acid Ester, stearyl acrylate, isostearyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, vinyl acetate, vinyl butyrate, vinyl propionate, ethylene isobutyrate Ester, vinyl valerate, vinyl neodecanoate, N-vinylpyrrolidone and N-vinyl caprolactam; preferably selected from the group consisting of acrylic acid Ester, stearyl acrylate, isostearyl acrylate, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl isobutyrate, vinyl valerate, vinyl neodecanoate, N-vinylpyrrolidone And N-ethylene caprolactam.

In a particularly preferred embodiment, no hydroxyalkyl (meth) acrylate is involved in the polymerization. It has been considered that the polymerization of the at least one (meth) acrylate monomer in the absence of hydroxyalkyl (meth) acrylate allows the supply of a particularly excellent comb copolymer (A).

In this polymerization, a particularly preferred user comprises acrylic acid, butyl acrylate, 2-ethylhexyl acrylate and acrylic acid. The mixture of esters is more preferably acrylic acid, butyl acrylate and 2-ethylhexyl acrylate.

The exemplary preferred mixture comprises from 3 to 7 weight percent acrylic acid, from 45 to 65 weight percent butyl acrylate, from 20 to 27 weight percent 2-ethylhexyl acrylate and up to 15 weight percent acrylic acid. The ester composition, the number by weight, is based on the total weight of the comonomer mixture and the at least one macromonomer, i.e., all of the constituents that contribute to the polymerization of the comb copolymer (A).

Macromonomer

The at least one (meth) acrylate unit system is polymerized in the presence of at least one macromonomer to form a comb copolymer (A). The macromolecular single system is a relatively low molecular weight polymer having reactive copolymerizable functional groups at one or more ends of the polymer. The at least one macromolecular monosystem is selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butene-propylene, and isobutylene macromonomers. These ethylene-butene, ethylene-propylene, ethylene-butene-propylene and isobutylene giants The macromonomer backbone of the molecular monomer is preferably fully hydrogenated. They can be obtained by anionic polymerization of the corresponding monomers. For example, one known method involves anionic polymerization to prepare a hydroxyl terminated, conjugated diene polymer of a monomer such as 1,3-butadiene and/or isoprene. Suitable rubbery mono-alcohols such as Kraton® L 1203 are available from Kraton Polymers Company. In a subsequent step, the terminal hydroxyl functional group can be reacted to form an acryloyl or methacryloxy group.

According to the invention, the macromonomer has a molecular weight of from 1000 to 500,000 g/mole, preferably from 2,000 to about 30,000 g/mol, more preferably from 2,000 to 10,000 g/mole (by gel permeation chromatography) (GPC) measurement, polystyrene as a standard, measurement method A1). In a preferred embodiment of the invention, the macromonomer has a glass transition temperature such as -30 ° C or lower, preferably from -70 ° C to -50 ° C, as measured by the DSC method. This macromolecular single system is commercially available, for example, from Kuraray Co., Ltd. A preferred macromolecular single system is from L-1253 of Kuraray Co., Ltd. As used herein, a macromolecular single system has a relatively low molecular mass, a functionally copolymerizable reactive group at one or more ends of the polymer, and more particularly, an acrylate functionality or A polymer of methacrylate functional groups.

Comb copolymer (A)

The comb copolymer (A) can be polymerized by radical polymerization of at least one (meth) acrylate monomer or a monomer comprising a (meth) acrylate monomer by the presence of at least one macromonomer. Obtained as a mixture of bodies. The comb copolymer (A) is a copolymer in the form of a comb, which is occasionally referred to as a "graft copolymer". However, in this context, the term "connects The branched copolymer" is misleading, wherein in the present example, the comb copolymer can be formed by polymerizing a comonomer of the comonomer mixture in the presence of a macromonomer. Thus, a substituted graft copolymerization exists. The polymer backbone provides a linkage attachment as a further monomer, as used herein, the side chain of the comb copolymer (A) is preferably copolymerizable between the comonomer and the macromonomer. a reactive group, preferably an acrylate functional or methacrylate functional group with the macromonomer, introduced during polymerization via the macromonomer chain. Furthermore, the macromonomer can be copolymerized The reactive group is incorporated into the polyacrylate backbone (backbone) during the actual polymerization of the comonomer mixture. The macromonomer is ethylene-butene, ethylene-propylene, ethylene-butene-propylene and / or isobutene chain forms the side chain of the comb copolymer (A) (also referred to herein as the hydrocarbon side chain of the comb copolymer (A)). Based on its structure, the comb copolymer (A ) is also referred to as a "bottle brush" polymer. Within the polymer composition (P) This structure and lipophilic nature of the hydrocarbon side chain results in the formation of a continuous acrylate phase and a discontinuous hydrocarbon phase Kw of the comb copolymer (A). The hydrocarbon phase Kw is preferably in the form of a microphase separation. Separating the comb-copolymer (A), which is preferably microphase-separated, combines different physical properties by the development of a continuous acrylate phase and a discontinuous hydrocarbon phase, these properties being particularly rubber-like in the side chain, in the present case Medium is hydrophobic, thermoplastic; inherent pressure-sensitive adhesive properties with polyacrylate backbone.

The component of the at least one macromonomer is from 1 to 50% by weight, preferably from 5 to 25% by weight and more preferably from 10 to 15% by weight, to participate in the overall composition of the polymerization of the comb copolymer (A). The total weight of the object is the basis. In other words, in the comb copolymer (A) The macromonomer unit constitutes 5 to 25 weight percent and preferably 10 to 15 weight percent based on the total weight of the comb copolymer (A).

In another preferred embodiment, the polymerization is carried out in the presence of at least one further non-polyolefin macromonomer. The additional non-polyolefin macromonomer is preferably selected from the group consisting of polymethacrylates, polystyrenes, polydimethyloxanes, polyethylene oxides, and polycyclic rings. Oxypropanes. These further non-polyolefin macromonomers are also macromonomers which are copolymerizable. In other words, these non-polyolefin macromonomers also preferably have functional acrylate or methacrylate groups at the end of the polymer chain of the macromonomer. In one embodiment of the invention, the at least one further non-polyolefin macromonomer has a component of up to 20, preferably up to 10, more preferably up to 5 weight percent, to participate in the total composition of the polymerization. The weight is the benchmark.

Hydrocarbon component (B)

The heterophasic polymer composition (P) comprises at least one hydrocarbon component (B), which in turn comprises at least one plasticizer resin soluble in the hydrocarbon phase of the comb copolymer (A) and at least one solid resin. In this context, the term "soluble" means not only a plasticizer resin but also a solid resin which is compatible with the hydrocarbon side chain of the comb copolymer (A), and thus in the polymer composition. A combined hydrocarbon phase Kw1 consisting of the hydrocarbon side chain of the comb copolymer (A) and the hydrocarbon component (B) is formed in (P). The presence of this combined hydrocarbon phase can be confirmed by the DSC method if the composition consisting of the comb copolymer (A) and the hydrocarbon component (B) differs from the DSC measurement before the component (B) is added. Only when the amount of static glass transition temperature of the comb copolymer (A) is There is no additional phase, which has been identified in the sense of additional static glass transition temperatures. Instead, the hydrocarbon phase of the polymer composition is characterized by its static glass transition temperature Tg (Kw1). This means that the hydrocarbon phase Kw1 from the side chain of the comb copolymer (A) and the component (B) has only one glass transition temperature Tg (Kw1) which is associated with the pure comb copolymer (A). Tg is different. If (B) is insoluble in the hydrocarbon phase Kw of the comb copolymer, two hydrocarbon phases Tgs, one hydrocarbon phase of the (pure) comb copolymer (A), and one system are detected. Component (B). Further, the acrylate phase of the acrylate skeleton participating in the comb copolymer (A) in the polymer composition is also determined by DSC in terms of its glass transition temperature (Tg (Ac)).

The hydrocarbon component (B) preferably comprises a solid resin (B1) and a plasticizer resin (B2), in each case having a number average molecular weight Mn (determined by GPC, method A1) is 1000 g/ Moor or less. For the purpose of the present invention, the solid resin is a hydrocarbon resin having a softening point of at least 70 ° C, preferably 70 to 150 ° C, more preferably 80 to 120 ° C. The plasticizer resin as used herein has a hydrocarbon resin having a softening point of not higher than 20 °C. The respective softening point of the solid and plasticizer resin is a ring & ball softening point (measured according to ASTM E28-99).

The hydrocarbon resins (B-1) and (B-2) preferably have a weight ratio of (B-1):(B-2) of 41:59 to 70:30. In a particularly preferred embodiment of the invention, the hydrocarbon resin (B-1) having a softening point of at least 70 ° C is present in an amount of from 41 to 70% by weight, more preferably from 50 to 60% by weight, The total amount of all hydrocarbon resins in the heterophasic polymer composition is based on the basis.

Suitable solid resins are petroleum-based synthetic hydrocarbons. Examples include resins based on aliphatic olefins. These resins are available from Cray Valley under the name of Wingtack® 95, from Exxon under the trade name of Escorez®, from Arakawa Chemical under the trade name Arkon® (P series), and from Hercules Speciality Chemicals to Regalrez® (1030, 2000 and 5000 series). The trade name is obtained under the trade name of Regalite® (R series) and from the Yasuhara Yushi Kogyo Company under the trade name Clearon®.

Suitable plasticizer resins are C5 resin Wingtack® 10 from Cray Valley, Dercolyte® LTG and fully hydrogenated hydrocarbon resins Regalite® 1010 and Piccotac® 1020.

In another embodiment of the present invention, the at least one hydrocarbon component (B) soluble in the hydrocarbon phase of the comb copolymer (A) is at least 80 in the hydrocarbon phase of the polymer composition. The weight percentage is based on the weight component of the hydrocarbon phase in the polymer composition, that is, based on the amount of the hydrocarbon side chain and the hydrocarbon component (B) of the comb copolymer (A), and its Tg ( Tg (Kw1)) can be determined by DSC.

It has been surprisingly revealed that the hydrocarbon resins (B-1) and (B-2) are particularly suitable for supply when (B-1) and (B-2) are present in an amount of 36 to 70 parts by weight. The polymer composition (P) is preferably 40 to 55 parts by weight based on 100 parts by weight of the polymer composition (P). In the case where the hydrocarbon compound (B-2) in the polymer composition (P) has a high component, an additional hydrocarbon phase Kw2 may be formed, which is additionally manifested to the hydrocarbon phase Kw1. A possible explanation for this is that the plasticizer resin (B-2) exceeds the solubility limit of the hydrocarbon in the comb copolymer (A) relative to the hydrocarbon compound (B-2). The amount is added. This additional hydrocarbon phase can be detected by dynamic mechanical analysis (DMA) according to ASTM D4065-12.

Additives and tackifying resins

In addition to the comb copolymer (A) and the hydrocarbon component (B) comprising at least one plasticizer resin and at least one solid resin, the polymer composition may comprise at least one additive and/or a tackifying resin. The additive as used herein comprises a plasticizer, an oil and a resin which are soluble in the acrylate phase of the comb copolymer (A), preferably a rosin ester and/or a terpene-phenol resin. Preferred rosin esters are hydrogenated rosin esters. A preferred terpene-phenol resin is an anti-aging terpene phenol resin.

It is also possible to add one or more tackifying resins which are different from the constituents of the hydrocarbon component (B). The use of a suitable tackifying resin such as, for example, a coumarin-coumarin resin allows fine adjustment of the static glass transition temperature Tg (Kw1) of the hydrocarbon phase in the polymer composition. The preferred amount of the additive and the tackifying resin, if present, is up to 20 parts by weight, more preferably up to 5 parts by weight, based on 100 parts by weight of the polymer composition (P). However, it has been revealed that the heterophasic polymer composition (P) develops a satisfactory bond strength with respect to the surface of the LSE material, even without the addition of a tackifying resin, and in particular without the addition of a soluble copolymer ( A) A resin of the acrylate phase. Furthermore, the multilayer article of the present invention does not even use this resin to ensure a durable high adhesion strength to the surface of the LSE material. Further, in the event that the resin soluble in the acrylate phase, if present, drifts from the heterophasic polymer composition (P) into the foam carrier (S) layer of the acrylate substrate The multilayer article of the present invention permits permanent adhesive bonding without causing a significant decrease in bond strength over time. The reason is The polymer composition (P) has inherently developed a satisfactory bond strength with respect to the surface of the LSE material.

In a further preferred embodiment, the polymer composition comprises an additional hydrocarbon compound (C) having a number average molecular weight (Mn) of greater than 1000 grams per mole. This additional hydrocarbon compound (C) is preferably a further plasticizer resin. In particular, the plasticizer resin of the polymer composition (P) and the solid resin each have a number average molecular weight Mn of 1000 g/mole or less, and the polymer composition (P) contains an additional hydrocarbon Compound (C) having a number average molecular weight Mn of more than 1000 g/mol is measured by a GPC method. In a particular embodiment of the invention, the hydrocarbon compound (C) forms a discontinuous phase within the acrylate phase of the polymer composition. In other words, in this particular embodiment, there are two different discontinuous phases within the continuous phase of the polymer composition. According to this embodiment, the static glass transition temperature Tg(C) of this additional phase in the polymer composition is between the glass transition temperatures Tg(Kw1) and Tg(Ac) of the polymer composition.

Further, an aging inhibitor, a photostabilizer, and an ozone protectant can be used as an additive. The aging inhibitor used may be an Irganox® product from BASF or a Hostanox® from Clariant, preferably a primary inhibitor, an example of 4-methoxyphenol or Irganox® 1076; and a secondary aging inhibitor, implemented Examples are Irgafos® TNPP or Irgafos® 168 from BASF, including combinations with each other. Other suitable aging inhibitors are thiophene (C radiation scavenger) and hydroquinone methyl ether also in the presence of oxygen, and oxygen itself. The light stabilizer used may be a UV absorber (Cyasorb® series) or a sterically hindered amine (Tinuvin® series).

In a preferred embodiment of the invention, the comb copolymer (A) or the heterophasic polymer composition (P) is crosslinked. Whenever possible, the crosslinking agent can be used, for example, the hydroxyl group, the anhydride or the caprolactam functional group in the acrylate phase of the comb copolymer can be used to push up the cohesive force of the polymer composition (P), particularly including Coordination or covalent bonding of chemical crosslinkers. The exemplary coordination crosslinking agents are metal chelates such as, for example, aluminum chelates and titanium chelates. Exemplary covalent crosslinkers that can be specifically used to push up high temperature shear strength are isocyanates, epoxides, oximes Aziridines, carbodiimides and Oxazolines. For the purposes of the present invention, the crosslinking agent is preferably used in an amount of from about 0.02 to about 2 weight percent based on the total weight of the comb copolymer (A).

Method for preparing the heterophasic polymer composition (P)

The polymer composition (P) can be obtained by first being at least one macromolecule selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene butene-propylene and isobutylene macromonomers. Prepared in the presence of a body to polymerize at least one monomeric mixture of a (meth) acrylate monomer or a monomer comprising at least one (meth) acrylate monomer described herein to form the comb copolymer (A) . The comb copolymer (A) can be prepared here by conventional polymerization techniques familiar to the skilled person. These methods include solutions, suspensions, emulsions, and bulk polymerization methods. The comb copolymer (A) is preferably prepared by radical polymerization in a solution. Preferred solvents and solvent mixtures ensure sufficient macromonomer solubility, and are ethyl acetate, acetone, methyl isopropyl ketone, hexane and/or heptane, and also toluene, and the solvents described. mixture. In a preferred embodiment of the invention, the residual monomer content is reduced after polymerization using methods known in the art.

After removing the solvent (if present), the acrylate backbone and the hydrocarbon side chain of the comb copolymer are preferably present in a phase separation structure in the form of a microphase separation structure, wherein the hydrocarbon phase Kw1 is copolymerized from the comb The hydrocarbon side chain of the substance (A) and at least one hydrocarbon component (B) soluble in the hydrocarbon phase are discontinuously present in the continuous acrylate phase of the polymer composition (P). In this context, "continuously" means that the acrylate phase surrounds a respective portion (also referred to as a region) of the discontinuous hydrocarbon phase as a substrate. The presence of the microphase-separated structure is revealed in the form of a transparent appearance of the polymer composition (P). In this polymer composition, the segment of the hydrocarbon phase has a size lower than the wavelength of visible light (390-780 nm).

Pressure sensitive adhesive

The invention further relates to a multilayer article wherein the polymer composition (P) is in the form of a pressure sensitive adhesive (PSA). It has surprisingly been found that the polymer composition (P) in the form of PSAs is particularly suitable for bonding substrates to non-polar surfaces. However, the PSAs of the present invention are still suitable for bonding polar surfaces. Non-polar surfaces are substrates having low surface energy or low surface tension, particularly having a surface tension of less than 45 millinewtons per meter, preferably less than 40 millinewtons per meter and more preferably less than 35 millinewtons. /meter. This surface tension is determined by measuring the contact angle by DIN EN 828.

The polymer composition (P) is preferably provided in the form of a film, more preferably an adhesive tape. For this purpose, the heterophasic polymer composition can be shaped from the solution by itself or after the addition of the tackifying resin, in a carrier material (film, foaming, composite microspheres). Forming a layer on the foam, fabric, paper), the PSA layer having a weight per unit area of 40 to 100 g/m2. It is particularly preferred to apply the heterophasic polymer composition (P) directly to the foam carrier (S) of the acrylate substrate.

The foamed vehicle carrier (S) of the acrylate substrate is described in more detail below.

Acrylate substrate foam carrier (S)

The multilayer article of the present invention comprises at least one layer of an acrylate substrate foaming carrier (S). The foam carrier (S) has an upper side and a lower side. The heterophasic polymer composition (P) described herein will be applied to at least one of these sides. In other words, at least one side of the sides is bonded to the heterophasic polymer composition (P). The heterophasic polymer composition (P) used herein will avoid the problem of the adhesive of the conventional acrylate substrate, wherein the adhesive of the conventional acrylate substrate must be provided as a mixture with the tackifying resin for bonding. To a non-polar surface. The reason for this is that the polymer composition (P) can develop a satisfactory adhesive strength with respect to the surface of the LSE material without even adding a tackifying resin soluble in the acrylate phase, and even without the aforementioned increase Adhesive resin retains these bond strengths. It has also been confirmed that the heterophasic polymer composition (P) is a one-phase stable system in which the composition of the hydrocarbon component (B) does not drift into the matrix of the foamed layer (S) of the acrylate substrate. . Furthermore, the use of the polymer composition (P) on the foam carrier support (S) layer of the acrylate substrate does not accompany the adhesion of a substrate having an LSE surface as expected with an adhesive of a typical acrylate substrate. The risk of loss of bond strength is lost over time, wherein the typical acrylate based adhesive develops its bond strength towards the LSE surface only by the use of a resin that is soluble in the acrylate phase of the adhesive.

At least one layer of the foam carrier (S) of the acrylate substrate comprises at least one acrylate, which is also referred to below as "acrylate of the foam carrier (S) layer forming the acrylate substrate", or as " An acrylate forming a foamed carrier layer (S) of an acrylate substrate, or an acrylate forming a layer of the foam carrier (S), or an acrylic acid forming a carrier layer of the foam Ester", or an analogue thereof. This acrylate can be converted into a foamed material by a known method to provide a foamed material of an acrylate substrate. Possible techniques include the use of a swelling agent; mixing with a swellable, pre-expanded, and fully expanded hollow sphere; or mixing with a non-expandable hollow sphere and introducing a gas.

In a preferred embodiment, the foam carrier support (S) of the acrylate substrate is a viscoelastic foam carrier. The foam carrier (S) of the acrylate substrate is preferably a composite microsphere foam. In the composite microsphere foam, glass microspheres or hollow ceramic spheres (microspheres) or microballoons are incorporated into the polymer matrix. Further, in the composite microsphere foam, the voids are separated from each other, and the substances (gas, air) present in the void are separated from the surrounding matrix by the film. This makes the material substantially stronger than the conventional foam containing non-reinforcing gas.

In another embodiment of the present invention, the acrylate forming the foam carrier (S) layer is a polyacrylic acid obtainable by free- or controlled-type radical polymerization of one or more acrylates and alkyl acrylates. ester. More preferably, the acrylate-based crosslinked polyacrylate which forms the foam carrier (S) layer.

The foamed vehicle carrier (S) of the acrylate substrate of the multilayer article of the present invention may contain not only the polyacrylate provided according to the present invention, but Also included are all polymers and/or mixtures of polymers known to those skilled in the art.

The foam carrier is preferably composed only of a polyacrylate such as a backbone polymer.

The polyacrylate of the foam carrier carrier (S) of the acrylate substrate can be preferably obtained by free- or controlled-type radical polymerization of one or more (meth)acrylic acid or (meth) acrylate, and more preferably For thermal crosslinking to prevent cross-linking gradients particularly in the case of thick foam carrier layers, this phenomenon can result from photochemical crosslinking methods or electron beam crosslinking.

In a preferred embodiment of the invention, the polymer of the thermally crosslinkable poly(meth)acrylate substrate is used in the foam carrier (S) layer. The acrylate forming the foam carrier (S) layer is preferably obtained by polymerization of a monomer composed of monomers from the following groups (a1), (a2) and (a3). "Polymerization" is used herein to mean a reaction which results in the polyacrylate being particularly suitable for forming a layer of the foamed carrier (S).

(a1) 70 to 100% by weight based on the acrylate and/or methacrylate and/or free acid of the formula (I), based on all monomers participating in the polymerization: Wherein R ¹ is H or CH ₃ ; and R ² represents H or C ₁ -C ₁₄ alkyl; "C ₁ -C ₁₄ alkyl" is in the present case referred to as an alkyl chain having 1 to 14 C atoms. The alkyl chain includes a linear group, that is, a linear group and a branched alkyl group; (a2) 0 to 30% by weight can be copolymerized with the monomer of the group (a1) and the olefin having at least one functional group is not a saturated monomer, based on all monomers participating in the polymerization; preferred "functional groups" of the monomers of group (a2) are polar and/or have anhydrides, substituted or unsubstituted aryl groups, aromatic a sterically bulky group of oxyalkyl and/or alkoxyalkyl functional groups, and also a heterocyclic group and an N,N-dialkylaminoalkyl unit; (a3) a further acrylate and/or Or a methacrylate and/or olefinically unsaturated monomer, preferably from 0 to 5% by weight, preferably from more than 0 to 5% by weight, copolymerizable with the monomer of group (a1) And having a functional group that causes covalent crosslinking by the coupling agent.

The group (a1) monomer used is preferably an acrylic monomer comprising an acrylate and a methacrylate having an alkyl chain of 1 to 14 C atoms. Preferred examples are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, acrylic acid. Amyl ester, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-decyl acrylate, lauryl acrylate, stearyl acrylate, stearyl methacrylate, acrylate and their fractions Isomers of the branches such as, for example, 2-ethylhexyl acrylate. Further examples which can be preferably used in small amounts as a group (a1) monomer are cyclohexyl methacrylate, acrylic acid Ester and methacrylic acid Esters. In each case, the component thereof is preferably at most up to 20% by weight, more preferably at most up to 15% by weight, based on the total amount of the monomers (a1).

Preferably, the group (a2) single system maleic anhydride, itaconic anhydride, glycidyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid Tert-butyl phenyl ester, butyl phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-butoxy acrylate Ethyl ester, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate and tetrahydrofurfuryl acrylate, and Also a mixture. It is also preferred to use as the group (a2) monomer an aromatic vinyl compound, wherein the aromatic core preferably contains a C ₄ to C ₁₈ group and may also include a hetero atom. Particularly preferred examples are styrene, 4-vinylpyridine, N-vinyl-indenylene, methylstyrene and 3,4-dimethoxystyrene monomers.

Preferred group (a3) monomers are hydroxyethyl acrylate, 3-hydroxypropyl acrylate, hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, methacrylic acid 4 - hydroxybutyl ester, allyl alcohol, itaconic acid, acrylamide and cyanoethyl methacrylate, cyanoethyl acrylate, 6-hydroxyhexyl methacrylate, N-tert-butyl butyl decylamine, N- Methylol methacrylamide, N-(butoxymethyl)methacrylamide, N-methylol acrylamide, N-(ethoxymethyl) acrylamide, N-isopropyl Acrylamide, vinyl acetate, β-propylene methoxypropionic acid, trichloroacrylic acid, fumaric acid, crotonic acid, aconitic acid, dimethacrylic acid, 4-vinylbenzoic acid, and mixtures thereof .

It is also advantageous to select particularly preferred monomers of group (a3) such that they comprise functional groups which support subsequent chemoradiation crosslinking (for example by electron beam or UV). Suitable copolymerizable photoinitiators are, for example, benzoin acrylate and acrylate functionalized diphenyl ketone derivatives. Things. The monomers which are crosslinked by electron beam bombardment of the support are, for example, tetrahydrofurfuryl acrylate, N-tert-butylbutyl decylamine and allyl acrylate. This list is not conclusive.

In a particularly preferred embodiment, the groups (a1) to (a3) are selected such that the resulting polymer is thermally crosslinkable; more particularly, the resulting polymer is possessed according to Donatas Pressure-sensitive adhesive properties of Satas Handbook of Pressure Sensitive Adhesive Technology (van Nostrand, New York, 1989).

The nature of the comonomer is chosen such that the glass transition temperature Tg(A) of the polymer is below the desired application temperature, and preferably at 15 °C or lower. In order to achieve this, it is preferred to select the amount of the composition of the monomer mixture comprising the monomers of groups (a1) to (a3) such that Fox equation (E1) (see TGFox, Bull. Am. Phys. Soc. 1956) 1,123) produces the desired Tg(A) value of the polymer.

In the equation, n represents the number of the monomer used, w _n represents the mass component (% by weight) of each monomer n, and T _{G, n} represents each of the homopolymers of the respective monomer n Do not change the temperature of the glass in K.

The Tg (A) (or "Tg" as in Equation E1 above) can be determined using the DSC method (measurement method A4).

In order to produce a suitable polyacrylate which can be used for the foam carrier (S) layer of the acrylate substrate, the monomer is preferably known by conventional means. The free radical polymerization or controlled radical polymerization proceeds to carry out the reaction. For carrying out the polymerization by a free radical mechanism, it is preferred to use an initiator system comprising a radical initiator which is further used for polymerization, more particularly a thermally decomposable radical to form azo or peroxygen. Starting agent. However, in principle, all common starters for acrylates and/or methacrylates which are familiar to the skilled person are suitable. The generation of C-center free radicals is described in Houben-Weyl, Methoden der Organischen Chemie, Vol. E 19a, pages 60 to 147. These technologies are prioritized for similarity.

Examples of such free radical sources are peroxides, hydroperoxides and azo compounds. Non-specific examples of typical free radical initiators are provided herein: potassium peroxydisulfate, benzammonium peroxide, cumene hydroperoxide, cyclohexanone peroxide, double-staged peroxidation Base, azobisisobutyronitrile, cyclohexyldecylethylene peroxide, diisopropyl percarbonate, butyl peroctoate and benzene alcohol. Particularly preferred for use as a free radical initiator are 2,2'-azobis(2-methylbutyronitrile) (Vazo® 67 from DuPont), 1,1'-azobis(cyclohexane) Carbononitrile) (Vazo® 88) and bis(4-tert-butylcyclohexyl) peroxydicarbonate (Perkadox® 16, from AkzoNobel).

It is very preferred to select the average molecular weights Mn and Mw of the polyacrylates which are formed by radical polymerization and which are useful as the acrylate of the foam carrier (S) of the acrylate substrate, such that they are in the range of 20,000 to 2,000,000 g/mole. Internally; it is preferred to produce an acrylate having a foaming material carrier (S) layer for an acrylate substrate having an average molecular weight Mw of 200,000 to 1,200,000 g/mole. The average molecular weight is determined by gel permeation chromatography (GPC).

The polymerization can be carried out in a large amount in the presence of one or more organic solvents in the presence of water or in a mixture of an organic solvent and water. The goal is to reduce the amount of solvent used. Suitable organic solvents are pure alkanes (for example, hexane, heptane, octane, isooctane), aromatic hydrocarbons (for example, benzene, toluene, xylene), esters (for example, ethyl acetate or propyl acetate). , butyl or hexyl ester), halogenated hydrocarbons (eg, chlorobenzene), alkanols (eg, methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether), ketones (eg, acetone and butyl) Ketones) and ethers (for example, diethyl ether and butyl ether) or mixtures thereof. The aqueous polymerization reaction can be combined with a water miscible or hydrophilic cosolvent to ensure that the reaction mixture is in a homogeneous form during monomer conversion. For the purposes of the present invention, cosolvents which are preferably used are selected from the group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidone. Classes, N-alkylpyrrolidones, polyethylene glycols, polypropylene glycols, decylamines, carboxylic acids and their salts, esters, organic thioethers, anthraquinones, anthraquinones, Alcohol derivatives, hydroxy ether derivatives, amino alcohols, ketones and the like, and also derivatives and mixtures thereof.

The polymerization time is dependent on the conversion and temperature, which is between four and 72 hours. The higher the optional reaction temperature, in other words, the higher the thermal stability of the reaction mixture, the lower the reaction time can be selected.

For thermally decomposable initiators, heat is introduced substantially to initiate the polymerization. For thermally decomposable initiators, the polymerization can be initiated by heating to 50 to 160 °C depending on the starting agent form.

Further, in the sense of the present invention, the chain transfer agent using the polymerization adjustment is also excellent, so that the polymerization can be carried out in a controlled manner and exert an influence on the mass distribution of the moir.

In this context, for free radical stabilization, a nitroxide can be used in a suitable procedure such as, for example, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PROXYL), 2 , 2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), derivatives of PROXYL or TEMPO, and other nitrooxides familiar to the skilled person.

A series of further polymerization methods can be selected from the prior art whereby an acrylate suitable for the foam carrier (S) layer of the acrylate substrate can be made using another procedure. Thus, WO 96/24620 A1 describes a polymerization process using very specific free radical compounds such as, for example, phosphorus-containing nitroxides which are predominantly imidazolium.

WO 98/44008 A1 discloses phenofolines, piperazine Ketones and piperazine A specific nitroxide group mainly composed of diketones.

DE 199 49 352 A1 describes heterocyclic alkoxyamines as regulators in the control of growth-type free radical polymerization.

Another controlled polymerization technique that can be advantageously used to synthesize block copolymers is atom transfer radical polymerization (ATRP), which uses preferably a monofunctional or difunctional secondary or tertiary halide as a starter. And extracting the halide, a halide of certain metal complexes. A variety of possible ATRP systems are further described in the patent specifications US 5,945,491 A, US 5,854,364 A and US 5,789,487 A.

The very good production operations carried out are various variations of RAFT polymerization (reversible addition fragmentation chain transfer polymerization). The polymerization process is described extensively, for example, in the patent specifications WO 98/01478 A1 and WO 99/31144 A1. It is particularly preferably suitable for the preparation of trisulfide carbonates having the general structure R'"-S-C(S)-S-R'" (Macromolecules 2000, 33, pp. 243-245).

In a very good variation, for example, the use of trisulfide carbonate (TTC1) and (TTC2) or sulfur compounds (THI1) and (THI2) to polymerize, wherein the ruthenium may be a phenyl ring, which may be unfunctionalized or Functionalized by alkyl or aryl substituents; linked directly or via an ester or ether bridge; or may be cyano or may be a saturated or unsaturated aliphatic group. The phenyl ring oxime may optionally carry one or more polymer blocks, such as, for example, polybutadiene, polyisoprene, polychloroprene or poly(meth) acrylate, which may have The architecture defined by P(A) or P(B), or polystyrene, exemplifies only a small portion. The functionalization can be, for example, a halogen, a hydroxyl group, an epoxy compound group, a nitrogen-containing or a sulfur-containing group, without which enumeration does not make any claims complete.

In connection with the above-mentioned polymerization by controlling the growth type free radical mechanism, it is preferred to further comprise an initiator system further comprising other radical initiators for polymerization, in particular the thermal decomposition already enumerated above. The type of free radical forms an azo or peroxygen initiator. However, in principle, all commonly used starters for acrylates and/or methacrylates are known to be suitable for these purposes. Furthermore, a source of free radicals that only release free radicals under UV irradiation can also be used.

The polyacrylate of the foam carrier (S) which can be obtained and preferably used to form the acrylate substrate by the method described can be mixed with at least one tackifying resin. According to a preferred embodiment of the invention, the resin is present in an amount between 0 and 40% by weight, based on the total composition, advantageously between 20 and 35% by weight. The tackifying resins which are intended to be used are those which are known and described in the literature.

More particularly, reference may be made to all aliphatic, aromatic and alkyl aromatic hydrocarbon resins, hydrocarbon resins based on pure monomers, hydrogenated hydrocarbon resins, functional hydrocarbon resins and natural resins. It is preferred to use α-pine oil, β-pine oil, and δ-limonene, anthraquinone resin, rosin, asymmetrical, hydrogenated, polymerized and esterified derivatives and salts thereof, terpene resins and terpene-phenol resins, and Also C ₅ , C ₅ /C ₉ , C ₉ and other hydrocarbon resins. Combinations of these with further resins can be used equally well to match the properties of the foamed carrier (S) layer of the resulting acrylate substrate to the requirements. It is particularly preferred to use all of the resins compatible (soluble) with the polyacrylate of the foam carrier (S) of the acrylate substrate. A particularly preferred procedure is the addition of terpene-phenol resins and/or rosin esters. The aforementioned tackifying resins can be used singly or in combination.

It is also possible to selectively use additives such as powdered and granulated fillers, dyes and pigments, in particular including these kinds of grinding and reinforcing products such as, for example, gas phase cerium oxide (Aerosils) (smoked cerium oxide) Class), chalk (CaCO ₃ ), titanium dioxide, zinc oxide and carbon black, and particularly in the case of melt processing, it can be used in a high proportion of 0.5 to 50% by weight to cause the acrylate substrate to be emitted. The overall formulation of the composition of the foam carrier (S) is based on the formulation. The use of gas-phase cerium oxide and various forms of chalk as a filler can be greatly preferred, and the use of Mikrosöhl chalk is particularly preferred. In a preferred ratio of up to 30% by weight, the adhesive properties of suitable acrylates (shear strength at RT, instantaneous bond strength to steel and PE) are not actually altered by the addition of a filler.

Further, particularly in the case of bulk polymerization and further processing from polymer melts, low combustion burn fillers such as, for example, ammonium polyphosphate; and also conductive fillers (such as, for example, conductive) may be added by mixing or incorporating. Carbon black, carbon fiber and/or silver coated beads; and also thermally conductive materials such as, for example, boron nitride, aluminum oxide and tantalum carbide; and also ferromagnetic additives such as, for example, iron (III) oxides. And also to increase the volume of additives, especially for the production of foamed layers and / or composite microspheres (such as bubblers, solid glass beads, hollow glass beads, carbonized beads, hollow phenolic beads, from other materials) Made microbeads, expandable microballoons (eg, Expancel® from AkzoNobel), ceria, citrate, renewable organic materials such as sawdust, organic and/or inorganic nanoparticles, and fibers); Also an aging inhibitor, a light stabilizer, an ozone protectant, a complexing agent and/or a swelling agent. The aging inhibitor which can be used preferably comprises not only a primary inhibitor such as, for example, 4-methoxyphenol or Irganox® 1076; but also a secondary inhibitor such as, for example, Irgafos® TNPP or Irgafos® 168 from BASF; a combination of each other. Here, reference will be made only to further corresponding Irganox® products from BASF and/or Hostanox® from Clariant. Other significant agents that can be used to combat aging include thiophene (C radical scavenger) and hydroquinone methyl ether also in the presence of oxygen, and also oxygen itself.

In a particularly preferred embodiment of the invention, the foam carrier (S) layer is foamed by the use of a microballoon. The microballoons are also known as expandable polymeric microspheres which are hollow elastic spheres having a thermoplastic polymer outer shell; moreover, they are also referred to as expandable polymeric microspheres. These balls are filled with a low boiling liquid or a liquefied gas. The outer shell material used more particularly includes polyacrylonitrile, polyvinyl dichloride (PVDC), polyvinyl chloride (PVC), polyamines or polyacrylates. Suitable low boiling liquids include, in particular, lower alkane hydrocarbons such as, for example, isobutane or isopentane, which are packaged under pressure into the polymer shell in the form of a liquefied gas. Due to the exposure of the microballoons, it is more particularly that the outer polymer shell softens on the one hand via thermal exposure, in particular by supplying heat or generating heat, by ultrasonic or microwave radiation. At the same time, the propellant liquid gas present in the outer casing is converted to its gaseous state. The microballoons undergo irreversible and three-dimensional expansion under specially matched pressures and temperatures. When the internal pressure is proportional to the external pressure, the expansion ends. Since the polymer outer shell is retained, a closed cell type foaming material is produced. In a preferred embodiment of the present invention, the foam carrier (S) of the acrylate substrate is produced by mixing acrylate and expandable polymer beads which form the foam carrier layer prior to expansion. .

Many heavy duty microballoons are commercially available, such as, for example, Expancel DU (dry unexpanded) products from Akzo Nobel, the difference being substantially in their size (6 to 45 microns in diameter in the unexpanded state) and their expansion The initial temperature required (75 ° C to 220 ° C).

Furthermore, it is also possible to obtain an unexpanded micro-balloon in the form of an aqueous dispersion having a solid content or a microballoon component of about 40 to 45% by weight. And a micro-balloon (parent mixture) also bounded by a polymer, such as in ethylene-vinyl acetate, wherein the microballoon concentration is about 65% by weight. A microballoon slurry system is additionally available, wherein the microballoons are present as an aqueous dispersion at a solids content of 60 to 80% by weight. According to an excellent development of the present invention, the microballoon dispersion, the microballoon slurry, and the parent mixture such as the DU product are suitable for foaming.

Foams made with microballoons have greater crack bridging capabilities than those filled with non-polymerizable non-polymeric hollow microspheres, such as hollow glass or ceramic beads, due to their flexible thermoplastic polymer outer shell. Therefore, they are more suitable for compensating for manufacturing tolerances. Furthermore, this type of foaming material is more capable of compensating for thermal stress.

In one embodiment of the invention, the acrylate of the foamed vehicle carrier forming the acrylate substrate may also be mixed or blended with other polymers after polymerization. Polymers based on natural rubber, synthetic rubber, vinyl aromatic block copolymers such as styrenic block copolymers, EVA, polyoxyxene rubber, acrylic rubber and polyvinyl ether possess suitable capabilities for this purpose. The polymer blends are made in solution or in an extruder, preferably in a multi-screw extruder or in a planetary roller mixer. In the case of a polymer blend, the acrylate component of the foam carrier (S) forming the acrylate substrate is preferably at least 50% by weight, more preferably at least 55% by weight, based on the foam carrier ( The total weight of all the constituents of S) is the basis. This ensures that the polymer composition (P) has sufficient adhesion to the foam carrier layer of the acrylate substrate and that satisfactory chemical resistance is ensured on the portion of the carrier.

Optionally, a conventional plasticizer (plasticizing agent), more particularly a concentration of up to 5% by weight, is added to the acrylate of the foam carrier carrier (S) layer forming the acrylate substrate, ie, to form An acrylate of the foam carrier carrier (S) of the acrylate substrate. The plasticizer used may be, for example, a low molecular weight polyacrylate, a phthalate, a water-soluble plasticizer, a plasticized resin, a phosphate, a polyphosphate, an adipate and/or a lemon. Acid salt.

The internal strength (cohesion) of the foam carrier carrier of the acrylate substrate, preferably the viscoelastic polyacrylate foam carrier, is preferably increased by crosslinking. For this purpose, a compatible crosslinker species can be optionally added to the above acrylate containing composition. Examples of crosslinking agents suitable for forming acrylates of the foam carrier support (S) layer of the acrylate substrate include metal chelates, polyfunctional isocyanates, polyfunctional amines, polyfunctional epoxys Compounds, polyfunctional oximes, polyfunctional oxazolines, polyfunctional carbodiimides or polyfunctional alcohols which react with functional groups which are reactive and present in the acrylate. Likewise, polyfunctional acrylates can be advantageously used as crosslinkers for actinic radiation.

The foam carrier support (S) layer of at least one layer of the acrylate substrate of the multilayer article of the present invention has a layer thickness of preferably at least 0.3 mm, more preferably at least 0.5 mm. Typical layer thicknesses of the foam layer range from 0.3 mm up to 5 mm, preferably from 0.5 mm up to 2 mm, even more preferably from 0.5 mm to 1.2 mm. The foamed carrier (S) layer of the acrylate substrate has a cell membrane structure, preferably a closed cell membrane structure, more preferably a composite microsphere foam structure, wherein 15% to 85% of the volume is occupied by voids.

The foam carrier carrier (S) layer of at least one layer of the acrylate substrate of the multilayer article of the present invention solves the problem, even without the tackifying resin (K), the additive (Ad) including the aforementioned filler, plasticizer (W) ) or additional polymer (P); and there is no K+Ad, K+W, K+P, Ad+W and other possible combinations of the two modes; and additionally, there is no K+Ad+W, K+Ad +P and other possible combinations of three ways; or no K+Ad+W+P. Further implementation of the method for producing a foam carrier (S) layer of an acrylate substrate

The foam carrier support (S) layer of at least one layer of the acrylate substrate of the multilayer article of the present invention can be made from a solution or solvent free from the melt. It is particularly preferred from the melt processing system, which allows for the production of a particularly thick layer of foamed material due to the lack of a drying step. A commonly used technique is suitable for foaming the acrylate of the foam carrier (S) layer forming the acrylate substrate. As described above, thermal crosslinking of the viscoelastic foam is desirable because it allows to avoid cross-linking gradients as compared to photochemical crosslinking or electron beam hardening. It is particularly preferred that the thermal crosslinking is achieved in accordance with the thermal method for the cross-linking of the polyacrylate melt, as specified in EP 0 752 435 A1 and EP 1 978 069 A1, which is expressly incorporated herein by reference. In the disclosure of the specification. However, the invention is not limited thereto. All cross-linking techniques familiar to the skilled person can also be used. In this context, for the purposes of the present invention, it is preferred to use a foaming technique that does not combat acrylate crosslinking of the foam carrier layer forming the acrylate substrate.

Furthermore, it is particularly preferred from the melt processing system because it allows the foaming operation to be controlled in a targeted manner, thus permitting optimization of the cell structure and also the density adjustment of the foam carrier. In particular, the foaming operation can This is advantageously carried out according to WO 2010/112346 A1, which is therefore expressly included in the disclosure of the present disclosure. However, the invention is not limited thereto.

Another very good specific example of the foaming operation in the present invention is the use of expandable polymer microbeads and the object of inhibiting foaming in an extrusion operation, which is only borrowed after leaving the mold. This causes the pressure generated by the departure to decrease.

Preferably, a method for suppressing foaming by expanding the expandable polymer beads in an extrusion operation is carried out as follows (refer to Figs. 1 and 2). The acrylate of the foamed carrier carrier (S) layer forming the acrylate substrate is melted and, in particular, transferred to the mixing assembly 2 by the transport assembly 1. In this assembly 2 and optionally in one or more further mixing assemblies 3 (suitable mixing assemblies 2, 3, in particular, extruders, such as double stud extruders and/or planetary rollers) In the machine, at the special metering points 22, 23, 34, 35 and 36, further essential components and, if appropriate, optional components, such as resins, accelerators, crosslinking agents, fillers and their like Analogs, and also micro balloons. If desired, at least one of the hybrid assembly 2, 3 or a further selectively provided assembly (not shown in the figures) is suitable for degassing the polymer melt. This degassing unit is not necessary, in particular, if all of the mixture composition has been degassed prior to addition and gas has been prevented from entering further. Advantageously, there is a vacuum dome V that is used to generate subatmospheric pressure that produces outgassing. In particular, the addition of a microballoon is carried out under elevated pressure to inhibit premature expansion of the hollow microbeads at the polymer melting temperature.

The molten mixture produced in this manner is transferred to the mold 5. When leaving from the mold 5, there is a pressure drop, and thus the hollow microbeads After it leaves, in other words, it expands after the pressure drop and ensures that the polymer composition foams. The composition foamed in this manner is then shaped, more particularly by a roller mill 4, such as a roller calender.

The method is set forth in more detail below with reference to the two figures, without any intention, and the teachings in accordance with the present invention should not necessarily be limited by this exemplary representation. In the figure: Figure 1 shows a particularly useful device architecture for performing the method; and Figure 2 is superimposed on a previously arranged device architecture, for example, showing the location assignment of the individual process steps, and additional In particular, temperature and pressure parameters.

The arrangement of the assembly and method apparatus, particularly the hybrid assembly, is shown by way of example and may vary depending on process conditions.

figure 1

In the first assembly 1, the polymer forming the foam carrier (S) layer forming the acrylate substrate is melted, for example, in a transport assembly such as an extruder (more particularly a single stud transfer extruder). And transporting the polymer melt, in particular by means of the transport assembly 1, via the connecting portion 11, more particularly the heatable connecting portion 11 (for example a hose or a conveying pipe) into the second assembly 2 More particularly, hybrid assemblies such as double stud extruders.

In the second assembly, additives such as, for example, all resins or certain resins, crosslinker systems or parts thereof (more particularly, cross-linking) may be combined with one another or separately via one or more metering points 22, 23 Additives and/or accelerators, fillers, color pastes or the like are added to the base polymer melt.

Degassing the thus blended polymer melt before exiting from the assembly 2, in other words, in particular from the double stud extruder, more particularly via a vacuum dome V at a pressure of 175 mbar Or lower, and then transferred through the second connecting portion 24, more particularly the heatable connecting portion 24 (eg, a hose or duct) into the third assembly 3, more particularly the second mixing The assembly, such as, for example, a planetary roller extruder that provides a sliding seal ring 36.

The third assembly 3, more particularly a planetary roller extruder, has one or more temperature controllable mixing zones 31, 32 and one or more syringe or metering devices 33, 34, 35 for introducing polymerization The melt is blended with further components and/or additives, the latter components and/or additives being more particularly degassed.

A resin or resin mixture is added via metering point 34, for example. Advantageously, the resin or resin mixture has previously been degassed in the respective vacuum dome V. Can be added to the embedded liquid via metering point 35 (here only graphically drawn at the same location as 34, however it can be sufficiently and at different metering points at different locations typically located on the extruder) balloon. The crosslinker system or part thereof (in particular, the component that has heretofore been lacking in the crosslinker system) is added via the same metering point or further metering point not shown in Figure 1. Advantageously, the crosslinker system or part thereof, more particularly the crosslinker and/or promoter, can be mixed with the microballoons, such as a microballoon/crosslinker system mixture. In the heated zone 32 (heatable mixing zone), the polymer melt is compounded with the added components and/or additives, but at least with the microballoons.

The resulting molten mixture is transferred into the mold 5 via a further joining section or a further transfer unit 37, such as, for example, a gear pump. Upon exiting from the mold 5, in other words, after the pressure drop, the incorporated micro-balloons expand, thus causing a foamed polymer composition, more particularly a foamed self-adhesive composition, It is subsequently shaped by a roll calender 4 (rollers 41, 42 and 43 of the calender; carrier material 44 on which the polymer layer is deposited) to form, for example, a film.

figure 2

The acrylate forming the foam carrier support (S) layer of the acrylate substrate is in the first assembly 1, as for example in a transport assembly such as an extruder (more particularly a single stud transfer extruder) Melting, and using the assembly, is transferred into the second assembly 2 as a polymer melt via a heatable hose 11 or similar connecting portion (eg, a transfer tube), such as, for example, a hybrid assembly such as a planet Roller extruder. In Fig. 2, a modularized planetary roller extruder having four modules is provided, which can control the temperature independently of each other (T ₁ , T ₂ , T ₃ , T ₄ ).

Further components may be added via the metering crucible 22, in particular a molten resin or a molten resin mixture (for better miscibility, it is preferred to select a high temperature in the section T ₂ and also preferably in the zone In segment T ₁ ). Additional additives or fillers, such as color pastes, may also be supplied, for example, via further metering, such as 22 (not separately drawn) presented in the assembly 2. A crosslinking agent can be preferably added at the metering point 23. Purpose, it is advantageous to lower the melting temperature for this was to reduce the reactive crosslinking agent and thus increases the working life (T ₄ lower temperature zone, it is advantageous also in that the low section T _3).

The polymer melt is transferred into the third assembly 3 by a heatable hose 24b or similar connecting portion and a melt pump 24a or another transfer unit, such as a further mixing assembly, such as, for example, a double stud The extruder is fed into the assembly 3 at location 33. For example, a promoter component is added at metering point 34. The design of the double stud extruder is advantageous so that it can be used as a degassing device. Thus, for example, at the position shown, the overall mixture can release all of the contained gas in the vacuum dome V at a pressure of 175 mbar or less. After the vacuum zone, there is a bulb B on the stud (the position of the throttle in the squeeze chamber, in particular forming a loop gap, such as an annular gap, for example, which is specially provided for adjustment in the extruder) The melt pressure) which allows pressure to build up in the subsequent section S. A pressure of 8 bar or more is established in the section S between the bulb B and the melt pump 37a by appropriately controlling the extruder speed and a transport unit downstream of the extruder, such as, for example, the melt pump 37a. In this section S, a microballoon mixture (microballoons embedded in a liquid) is introduced at the metering point 35, and uniformly incorporated into the polymer composition in the extruder.

The resulting molten mixture is transferred into the mold 5 by a transfer unit (melting pump 37a and connecting portion 37b such as, for example, a hose). Upon exiting from the mould 5, in other words, after the pressure drop, the incorporated microballoons expand, thus forming a foamed polymer composition, more particularly a foamed carrier layer S, which is subsequently shaped By the calender calender 4, for example, a film is formed.

Furthermore, the foam carrier (S) forming the acrylate substrate can be formed using all chemical and physical foaming methods familiar to the skilled person. The acrylate of the layer is converted into a foaming material. However, if necessary, it should be ensured that the acrylate of the foam carrier (S) layer forming the acrylate substrate is still thermally crosslinkable.

In a further aspect, the present invention is directed to a method for making a multilayer article of the present invention comprising: (i) providing a foam carrier (S) having an upper and a bottom acrylate substrate as described herein. And (ii) applying the heterophasic polymer composition (P) described herein to the top and/or bottom of the foam carrier (S).

The step (i) of the method of the present invention preferably comprises the following steps: (a) providing one or more acrylates and alkyl acrylates which are polymerizable by free-form or controlled-type radical polymerization; (b) polymerization The acrylate and alkyl acrylate provided in process step (a) to form the polyacrylate described herein; and (c) converting the resulting polyacrylate to the polyacrylic acid described herein An ester foaming material, preferably a polyacrylate produced by foaming to form the polyacrylate foaming material, more preferably cross-linking and foaming or foaming and crosslinking the polyacrylate to form a crosslinked a polyacrylate foam; and (d) the polyacrylate foam is formed into a foam carrier (S) layer as described herein.

In view of the suitable ability of the heterophasic polymer composition (P) described herein to bond adhesively to articles, and more particularly to the gluing of articles having a low energy surface, the present invention is more One kind An adhesive tape comprising the multilayer article of the present invention, and also relates to the use of the multilayer article for gluing adhesive articles, and more particularly for gluing and bonding surfaces having low energy.

The multilayer articles of the present invention are particularly suitable for gluing and bonding different materials and components, such as badges, molded parts made of plastic (e.g., bumpers), and rubber seals on motor vehicle bodies. In particular, in this case, the bonding may also be performed only after the body coating LSE varnishing step, providing the low energy material properties of the body surface.

In the following, the invention will be elucidated in more detail with reference to particular embodiments.

Example Measurement method (general): K value (according to Fikentscher) (method A1):

The K value is the average molecular size measurement in the polymer compound. For this measurement, a percentage strength (1 g/100 ml) toluenic polymer solution was prepared and the Vogel-Ossag viscometer was used to determine its kinetic viscosity. After normalizing the toluene viscosity, the relative viscosity is obtained and the K value can be calculated according to the use of Fikentscher (Polymer 1967, 8,381 ff.).

Gel Permeation Chromatography GPC (Method A2):

In this patent specification, the numbers for weight average molecular weight Mw and polydispersity (PD) are determined by gel permeation chromatography. The decision was made on 100 microliters of sample that had been subjected to purification filtration (sample concentration 4 g/l). The extract used was tetrahydrofuran having 0.1% by volume of trifluoroacetic acid. The measurement was carried out at 25 °C. The preparatory column used was a PSS-SDV column, 5 microns, 10 ³ angstroms, ID 8.0 mm x 50 mm. Separation system using column PSS-SDV, 5 micron, 10 ³ Egypt, 10 ⁵ Egypt, 10 ⁶ angstroms, each ID 8.0 mm x 300 mm (column from Polymer Standards Service; detected using Shodex RI71 differential refractor) . The flow rate is 1.0 ml per minute. Correction was performed against the PMMA standard (polymethyl methacrylate correction).

Solids content (Method A3):

The solids content is a measure of the component of the non-evaporable constituents in the polymer solution. The weight of the solution was determined, and the solution was weighed, and then the evaporated component was evaporated in a drying cabinet at 120 ° C for 2 hours, and the residue was weighed again.

Static glass transition temperature Tg (method A4):

The static glass transition temperature is determined by a dynamic scanning card according to DIN 53765. The figures provided for the glass transition temperature Tg are related to the glass transition temperature value Tg according to DIN 53765:1994-03, unless otherwise indicated.

Density is determined by the pycnometer (Method A5a):

The measurement principle is based on the displacement of the liquid located in the pycnometer. First, the empty pycnometer or the liquid filled pycnometer is weighed, and then the body to be measured is placed in the container.

Calculate the density of the bulk from the difference in weight: Assume: ̇ m ₀ is the mass of the empty pycnometer, ̇ m ₁ is the mass of the pycnometer filled with water, ̇ m ₂ is the mass of the pycnometer and the solid body, ̇ m ₃ The mass of the water-filled pycnometer and the solid body, ̇ ρ _w is the density of the water at the corresponding temperature, and the density of the ̇ ρ _F- based solid body.

The density of the solid body is then provided by:

Each sample was assayed in triplicate. It should be noted that this method provides an unadjusted density (in the case of a porous solid body, in this case a foamed material, which is based on the volume including the pores).

A quick method to determine density from coating weight and layer thickness (Method A5b):

The weight or density per unit volume of the applied layer is determined by the ratio of the weight per unit area to the individual film thickness:

MA = coating weight / weight per unit area (excluding liner weight) in [kg / m ^ 2 ]

d = layer thickness (excluding pad thickness) in [meters]

This method also provides an unadjusted density.

In particular, this density determination is suitable for determining the finished product, including the total density of the multilayer article.

Measurement methods (especially PSAs): 180° bond strength test (method H1):

An acrylate PSA having a width of 20 mm applied to the polyester was applied in one layer to a steel plate which had been previously washed twice with acetone and once with isopropyl alcohol. The pressure sensitive adhesive strip was pressed onto the substrate with a pressure of 2 kg applied twice. The tape was then immediately removed from the substrate at a speed of 300 mm/min and at an angle of 180°. All measurements were taken at room temperature.

The results are reported in Newtons/cm and have been averaged from three measurements. The adhesion strength to polyethylene (PE) and varnish was measured in the same manner. In each case, for example also measured by method H2, the varnish used was from U.S. U.S. Patent No. FF79-0060 0900.

90° bond strength to steel - open and lining (method H2):

The bond strength to steel is determined by testing at temperatures of 23 ° C +/- 1 ° C and 50% +/- 5% relative atmospheric humidity. The sample was cut to a width of 20 mm and adhered to the steel plate. Clean and condition the steel plate before measuring. This was done by first wiping the plate with acetone and then leaving it in the air for 5 minutes so that the solvent could evaporate. The 50 micron aluminum foil was then lined on the side of the three-layer assembly facing the test substrate to prevent the sample from stretching during the measurement. After that, the test sample was rolled onto a steel substrate. For this purpose, the 2 kg roller was returned five times on the tape at a rolling speed of 10 meters per minute. Immediately after rolling, the steel plate was inserted into a special base which allowed the sample to be peeled up vertically at an angle of 90°. Adhesion strength measurements were made using a tensile strength tester from Zwick. When the inner lining is applied to the steel sheet, the open side of the three-layer assembly is first laminated to the 50 micron aluminum foil, the release material is removed and the assembly is adhered to the steel sheet, similarly rolled and subjected to measurement.

Measurements of the open and lining sides were reported in Newtons/cm, and averaged from three measurements.

Retention (PSA on PET film, method H3):

A strip of tape 13 mm wide and more than 20 mm long (eg, 30 mm) is applied to a smooth steel surface that has been cleaned three times with acetone and once with isopropyl alcohol. The bond area is 20 mm x 13 mm (length x width) with which the test panel is suspended (for example, 10 mm according to the 30 mm length described above). Then, the tape was pressed onto the steel carrier four times with a corresponding weight of 2 kg. Hang the sample vertically so that the protruding end of the tape points down. A weight of 1 kg was attached to the protruding end of the tape at room temperature. The measurement was carried out in a heating cabinet under standard conditions (23 ° C +/- 1 ° C, 55% +/- 5% atmospheric humidity) and at 70 ° C. For this measurement, the sample was loaded with a weight of 0.5 kg.

The measured retention (the time elapsed before the tape was completely separated from the substrate; the measurement was interrupted after 10,000 minutes) was reported in minutes and corresponded to the average of the three measurements.

Retention - open and inner lining (tape object, method H4):

Sample preparation was carried out under test conditions of 23 ° C +/- 1 ° C temperature and 50% +/- 5% relative atmospheric humidity. The test sample was cut to 13 mm and adhered to the steel plate. The bonding area is 20 mm x 13 mm (length x width). Clean and condition the steel plate before measurement. This was done by first wiping the plate with acetone and then leaving it in the air for 5 minutes to allow the solvent to evaporate. After the bonding has been made, the open side is reinforced with 50 micron aluminum foil and passed back and forth twice on the assembly with a 2 kilogram roll. The belt loop is then placed over the projecting end of the three-layer assembly. Of course After that, hang the system with the appropriate equipment and accept it for 10 Newtons. The type of suspension device is such that the sample is subjected to a weight load at an angle of 179 ° +/- 1 °. This ensures that the three-layer assembly cannot be stripped from the bottom edge of the panel. The measured retention is reported in minutes between the time the sample is suspended and its fall, and corresponds to the average from three measurements. For the measurement of the liner side, the open side was first reinforced with 50 micron aluminum foil, the release material was removed, and the sample was adhered to the test panel in a manner similar to the open side. Measurements were carried out under standard conditions (23 ° C, 55% humidity).

Dynamic shear strength (method H5):

A square adhesive transfer tape having an edge length of 25 mm was bonded between the two steel sheets and pressed downward at 0.9 kN (force P) for 1 minute. After 24 hours of storage, the assembly was separated using a tensile test machine from Zwick at 50 mm/min and at 23 ° C and 50% relative humidity, which was opened in such a way as to be at an angle of 180° to each other. Two sheets of steel. The maximum force is measured in Newtons per square centimeter.

Especially for the resistance of 60/95spirit, engine oil and diesel (method H6):

Samples were prepared and measured as in Method H1. The already bonded sample was placed in the study solvent which had been conditioned at 23 °C for 10 minutes. Then, the sample was taken out from the solvent bath and wiped down, and the residual solvent was evaporated for more than 10 minutes, after which it was measured by comparison with a sample having the same tape that was not held in the solvent and having the same contact time with the substrate. Bond strength.

The following table includes commercially available chemicals used in the examples described herein.

Preparation of I Comb Copolymer (A) - P1 to P4

The preparation of the exemplary comb copolymer (A) is described below.

Example P1:

A 100 liter glass reactor for radical polymerization was charged with 1.2 kg of acrylic acid (AA, 3%), 20.97 kg of 2-ethylhexyl acrylate (EHA, 52.43%), and 9.83 kg of butyl acrylate (BA, 24.57%), 4.0 kg of acrylic acid Ester (IBOA, 10%), 4.0 kg of macromonomer L-1253 (10%) and 20.8 kg of acetone/60/95 spirit (1:1). After the nitrogen had passed through the reactor for 45 minutes, the reactor was heated to a maximum of 58 ° C with stirring and 0.8 kg of Vazo® 67 was added. Thereafter, the external heating bath was heated to 75 ° C and the reaction was continued at this external temperature. After 1 hour of reaction time, 0.8 kg of Vazo® 67 was further added. During the 5 hours (counted from the last addition to Vazo® 67), the dilution was increased by 5.0 to 10.0 kg 60/95 spirit per hour, and this was ensured for proper mixing. In order to reduce the residual degree of the monomer, after adding 6 kg of peroxydicarbonate double (4-tridecyl) each time after 6 hours and 7 hours from the start of the reaction (that is, counting from the first addition of Vazo® 67). Base cyclohexyl) ester, diluted between 15 kg 60/95 spirit. After 24 hours of reaction time, the reaction was interrupted by cooling to room temperature.

Comb copolymer (A)-P2 to P4

Comb copolymers P2 to P4 were prepared as in Example P1. The mass percent numerical series for each monomer used is in Table 1. Ethyl acetate was used for the polymerization of the hybrid polymer P3 and for all dilutions performed during the preparation of P3.

Table 2 shows the molar mass distribution of the hybrid polymers P1 to P4 as measured by GPC and the static glass transition temperature as measured by DSC.

Preparation of II heterophasic polymer composition (P)-PSA 1 to PSA 4 and comparative compositions VPSA 5 to VPSA 7

The preparation of the exemplary heterophasic polymer composition (P) is described below. All Examples PSA 1 to PSA 4 and also Comparative Examples VPSA 5 to VPSA 7 were prepared as solutions and then coated onto a 36 micron PET film (Kemafoil HPH 100, Covema) or onto a deuterated release film for lamination to The foam carrier layer of the acrylate substrate is subsequently dried. In each case, the coating weight was 50 g/m 2 .

The heterophasic polymer compositions PSA 1 to PSA 4 and also the comparative example VPSA 5 are mainly composed of an acrylate hydrocarbon mixed polymer, which is prepared as a solution from the mixed polymers P1 to P4. For this purpose, they were diluted to a solids content of 30% with spirit, 0.3% by weight of an aluminum acetonate pyruvate crosslinking agent and a resin according to Table 3 were added to the solution, followed by coating and subsequent drying. For coating and drying, use a dry zone with different temperature zones The dry tunnel is set up after the comma bar (coating rate 2.5 m / min, dry tunnel 15 m, temperature - zone 1:40 ° C, zone 2: 70 ° C, zone 3: 95 ° C, zone 4: 105 ° C).

The resin component and glass transition temperature series of the acrylate phase and hydrocarbon phase of the heterophasic polymer composition (P) are shown in Table 3; technical adhesive materials such as PSA 1 to PSA 4 and also comparative examples VPSA 5 to VPSA 7 series In Table 4.

Comparative Example - Crosslinked Synthetic Rubber PSA (VPSA 6):

For the comparative example PSA 5, 33.0 kg of Kraton D 1101, 17 kg of Kraton D 1118, 48.0 kg of Escorez 2203 hydrocarbon resin and 2.0 kg of Shellflex 371 oil were dissolved in 100 kg of toluene. After coating (film thickness: 50 g/m2) and drying, the material was additionally crosslinked by electron beam hardening (EBC). This electron beam hardening was carried out using a unit from Electron Crosslinking AB (Halmstad, Sweden (Sweden)), and using an accelerator voltage of 220 keV and a dose of 35 kGy and a conveyor speed of 3 m/min.

Comparative Example - Polyacrylate PSA (VPSA 7):

A 100 liter glass reactor for radical polymerization was charged with 2.0 kg of acrylic acid, 25.0 kg of butyl acrylate, 13.0 kg of 2-ethylhexyl acrylate and 26.7 kg of acetone/60/95 spirit (1:1). After nitrogen had passed through the reactor for 45 minutes, the reactor was heated to a maximum of 58 ° C with stirring and 30 grams of AIBN was added. After that, the external heating bath was heated to 75 ° C and the reaction was continued at this external temperature. After a reaction time of 1 hour, a further 30 grams of AIBN was added. After 4 hours and 8 hours, each time a 10 kg acetone/60/95 spirit (1:1) mixture was diluted. In order to reduce the residual agent residue, after 8 hours and again after 10 hours, a 90 g portion of bis(4-tert-butylcyclohexyl)peroxydicarbonate was added. After 24 hours, the reaction was terminated by cooling to room temperature. The resulting polyacrylate had a K value of 49.3, an average molecular weight of Mw = 1058800 g/mole, a polymerization dispersibility PD (Mw/Mn) = 15.1, and a static glass transition temperature of Tg = -15.3 °C. Subsequently, the polyacrylate was made with 0.2% by weight Uvacure 1500 Blend, diluted to a solids content of 30% with acetone, and then applied from the solution onto a deuterated release film (50 micron polyester) or onto a 23 micron etched PET film. (Coating rate 2.5 m/min, drying tunnel 15 m, temperature-area 1:40 ° C, zone 2: 70 ° C, zone 3: 95 ° C, zone 4: 105 ° C). The coating weight is 50 g/m 2 .

Bond strength (BS) measurements, instantaneous, by method H1; retention force (HP) time measurements were performed by method H3 at room temperature. A: Adhesive component, K: cohesive fracture.

III. Preparation of Exemplary Polyacrylate-VT 1 and VT 2 for the Foam Carrier (S) Layer of the Acrylate Substrate

The preparation of the starting polymer is described below. The polymers studied are conventionally prepared as solutions via free radical polymerization.

Polyacrylate VT 1

The conventional reactor for radical polymerization was charged with 54.4 kg of 2-ethylhexyl acrylate, 20.0 kg of methyl acrylate, 5.6 kg of acrylic acid and 53.3 kg of acetone/isopropanol (94:6). After the nitrogen had passed through the reactor for 45 minutes, the reactor was heated to a maximum of 58 ° C with stirring and 40 g of 2,2'-azobis(2-methylbutyronitrile) was added. Thereafter, the external heating bath is heated to 75 ° C and continues at this external temperature. The reaction. After 1 hour, a further 40 g of 2,2'-azobis(2-methylbutyronitrile) was added, and after 4 hours, it was diluted with 10 kg of an acetone/isopropanol mixture (94:6).

After 5 hours and again after 7 hours, a further restart was carried out with 120 g of bis(4-tert-butylcyclohexyl)peroxydicarbonate. After 22 hours of reaction time, it was cooled to room temperature. The polyacrylate had a K value of 58.8, a solid content of 55.9%, an average molecular weight of Mw = 746,000 g/mole, a polymerization dispersibility (Mw/Mn) = 8.9, and a static glass transition temperature of Tg = -11.0 °C.

Polyacrylate VT 2

The conventional reactor for radical polymerization was charged with 30 kg of 2-ethylhexyl acrylate, 67 kg of n-butyl acrylate, 3 kg of acrylic acid and 66 kg of acetone/isopropanol (96:4). After the nitrogen had passed through the reactor for 45 minutes, the reactor was heated to a maximum of 58 ° C with stirring and 50 g of 2,2'-azobis(2-methylbutyronitrile) was added. Thereafter, the external heating bath was heated to 75 ° C and the reaction was continued at this external temperature. After 1 hour, further 50 g of 2,2'-azobis(2-methylbutyronitrile) was added, and after 4 hours, it was diluted with 20 kg of acetone/isopropanol mixture (96:4).

After 5 hours and again after 7 hours, it was re-started with 150 g of bis(4-tert-butylcyclohexyl)peroxydicarbonate and diluted with 23 kg of acetone/isopropanol mixture (96:4). . After 22 hours of reaction time, the polymerization was interrupted by cooling to room temperature. The polyacrylate had a K value of 75.1, a solid content of 50.2%, an average molecular weight Mw of 148,000 g/mole, a polymerization dispersibility (Mw/Mn) of 16.1, and a static glass transition temperature of Tg = -38.5 °C.

IV micro-balloon mixture manufacturing

The microballoons were placed in a container that had been filled with Reofos® RDP as a liquid component (dispersant) as reported in the various examples. Then, the mixture was stirred at a rotation speed of 600 rpm for 30 minutes at a pressure of 5 mbar in a planetary agitator mechanism from PC-LABORSYSTEM.

Method 1: Concentration/Preparation of Polyacrylate Molten

The acrylate copolymer (base polymer VT 1 and VT 2) is released from the solvent by a single stud extruder (Extrusion Feeder 1, Troester GmbH & Co KG, Germany) (residual Solvent content 0.3% by weight; refer to the respective examples). The parameters provided by the examples herein are those for the concentration of polyacrylate VT 1 . The stud speed is 150 rpm, the motor current is 15 amps and the throughput of 60.0 kg liquid/hour is achieved. For concentration, a vacuum is applied at three different domes. The reduced pressure ranges from 20 mbar to 300 mbar. The outlet temperature of the concentrated hot melt is about 115 °C. The solids content after this concentration step was 99.8%.

Method 2: Preparation of foaming composition

Foaming was carried out in an experimental unit corresponding to the clarification in Fig. 2. According to method 1, the corresponding polyacrylates (VT 1 and VT 2) are melted in the feeder extruder 1 and, by means of the extruder, are transported as polymer melts via the heatable hose 11. Entering Planetary Roller Extruder 2 (PRE) from Entex (Bochum) (more specifically, using PRE with four modules T ₁ , T ₂ , T ₃ and T _{4 that} can be heated independently of each other) in. Via the metering crucible 22, there is the possibility of supplying additional additives or fillers, such as, for example, a color paste. A crosslinking agent is added at position 23. All components are mixed to form a uniform polymer melt.

The polymer melt is transferred into a double stud extruder 3 (from Berstorff) (feed position 33) by a melt pump 24a and a heatable hose 24b. The accelerator component is added at position 34. Subsequently, the entire mixture releases all of the contained gas in a vacuum dome V at a pressure of 175 mbar (free of gas, see above). Below the vacuum zone there is a bulb B on the stud which allows pressure to build up in the subsequent section S. By appropriately controlling the extruder speed and the melting pump 37a, a pressure greater than 8 bar is established in the section S between the bulb B and the melt pump 37a, and a microballoon mixture is added at the metering point 35 (the microballoon is based on The details provided in the experimental series are embedded in the dispersion aid) and uniformly incorporated into the premix by mixing elements. The resulting molten mixture is transferred into the mold 5.

After exiting from the mold 5, in other words, after the pressure drop, the incorporated microballoons expand, and the pressure drop produces low shear, more particularly no shear, cooling the polymer composition. This produces a froth of an acrylate substrate which is subsequently applied between two release materials to form a foam carrier (S) layer of the acrylate substrate, more particularly after reuse. The release material (in the process of the liner) and the film formed by the roller calender 4 are formed.

V multilayer product MT 1 to MT 8; Comparative Example VMT 9 to VMT 11

In all of the examples, the same PSA was applied to both sides of the foam carrier of the acrylate substrate. In all cases, the coating weight of the respective heterophasic polymer composition on the viscoelastic support was 50 g/m 2 .

In order to improve the fixation of the PSA on the shaped viscoelastic carrier layer, not only the PSA but also the viscoelastic carrier is corona treated before the lamination step (corona unit from Vitaphone, Denmark). 100 watts per minute / square meter). This treatment results in improved chemical attachment to the viscoelastic carrier layer after the three layer assembly has been fabricated. The diaphragm speed is 30 meters per minute when moving through the laminate unit. Prior to lamination, any anti-adhesive carrier is removed, more particularly in the in-process liner, and the completed three layer product is wound with the remaining second anti-adhesion carrier.

The following specific embodiments of the multilayer article (MT) of the present invention and also the comparative product (VMT) of the invention are not shown, without any intention to specify the formulation, configuration, operating parameters and/or product design specified in detail. Unnecessary restrictions are imposed on the invention.

Stripping increase behavior of VI three-layer product MT 6 and comparative example VMT 9 to VMT 11

Stability of VII three-layer product MT 6 and also comparative example VMT 9 to VMT 11 to 60/95spirit

Preferred embodiment of the invention

The following general organization is a particularly preferred embodiment of the invention, which is in the form of specific examples EMB 1 to EMB 31:

EMB 1. A multilayer article comprising: - a foam carrier support (S) of at least one acrylate substrate; and - a heterophasic polymer composition (P) applied to the layer; the heterophasic polymer composition (P) comprising : ○ a comb-shaped copolymer (A) which can be obtained by at least one selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butylene-propylene and isobutylene macromonomers. In the presence of macromonomers, Polymerizing at least one (meth) acrylate monomer, and forming a continuous acrylate phase with a discontinuous hydrocarbon phase Kw; ○ and at least one hydrocarbon component (B), which is soluble in the comb The hydrocarbon phase Kw of the copolymer (A) comprises at least one plasticizer resin and at least one solid resin; the heterophasic polymer composition (P) has a continuous acrylate phase having a static glass transition temperature Tg (Ac), which is measured by the DSC method; and a discontinuous hydrocarbon phase Kw1 comprising the hydrocarbon component (B) and having a static glass transition temperature Tg (Kw1), which is measured by the DSC method, Wherein Tg(Kw1) is 35 to 60 grams of errone, more preferably 40 to 60 grams of oturology, more preferably 45 to 60 grams of otography, higher than Tg(Ac).

EMB 2. For a multilayer article of EMB 1, the foamed carrier (S) of the acrylate substrate is a viscoelastic foam carrier.

EMB 3. The multilayered article according to any one of the aforementioned EMB 1 and EMB 2, wherein the acrylate forming the foam carrier (S) layer is a polyacrylate which can be free-radically polymerized by free or controlled type of one or more acrylic acids. Obtained with esters and alkyl acrylates.

EMB 4. The multilayered article according to any one of the aforementioned EMB 1 to EMB 3, wherein the acrylate forming the foam carrier (S) layer is a crosslinked polyacrylate, preferably a thermally crosslinked polyacrylate.

EMB 5. The multilayered article according to any one of the aforementioned EMB 1 to EMB 4, wherein the acrylate forming the foam carrier (S) layer is a polyacrylate which can be polymerized by the following groups (a1) to (a3) Monomer consisting of monomers obtained: (a1) 70 to 100% by weight of acrylates and/or methacrylates and/or free acids according to formula (I) to participate in all monomers of the polymerization For the benchmark:

Wherein R ¹ is H or CH ₃ ; and R ² represents H or C ₁ -C ₁₄ alkyl; (a2) 0 to 30% by weight of an olefinically unsaturated monomer which is copolymerizable with the monomer of group (a1) Polymerizing and having at least one functional group based on all monomers participating in the polymerization; and (a3) selectively further acrylate and/or methacrylate and/or olefinically unsaturated monomers, preferably from 0 to 5 The component by weight %, based on all monomers participating in the polymerization, can be copolymerized with the monomer of group (a1) and have at least one functional group which is covalently crosslinked by the coupling agent.

EMB 6. For a multilayer article of EMB 5, the single system of the group (a1) is selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, N-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-decyl acrylate, lauryl acrylate, stearyl acrylate , stearyl methacrylate, acrylate and its branched isomers such as, for example, 2-ethylhexyl acrylate, and mixtures thereof; and/or the single system of the group (a2) is selected from The following: maleic anhydride, itaconic anhydride, glycidyl methacrylate, benzyl acrylate, methyl Benzyl acrylate, phenyl acrylate, phenyl methacrylate, butyl phenyl acrylate, butyl phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, methyl 2-butoxyethyl acrylate, 2-butoxyethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, acrylic acid Diethylaminoethyl ethyl ester and tetrahydrofurfuryl acrylate, and also mixtures thereof; and/or the single system of group (a3) is selected from the group consisting of: hydroxyethyl acrylate, 3-hydroxypropyl acrylate, A Hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl alcohol, itaconic acid, acrylamide and cyanoethyl methacrylate, Cyanoethyl acrylate, 6-hydroxyhexyl methacrylate, N-tert-butyl butyl decylamine, N-methylol methacrylamide, N-(butoxymethyl)methacrylamide, N-methylol acrylamide, N-(ethoxymethyl) acrylamide, N-isopropyl acrylamide, vinyl acetate, β-propylene methoxy propionic acid, trichloropropyl Acid, fumaric acid, crotonic acid, aconitic acid, dimethyl acrylic acid and 4-vinylbenzoic acid, and also mixtures thereof.

EMB 7. A multilayer article according to any one of the aforementioned EMB 1 to EMB 6, which is a tape.

EMB 8. For a multilayer article according to any one of EMB 5 to EMB 7, the monomers of groups (a1) to (a3) are selected such that the static glass transition temperature Tg of the acrylate forming the foam carrier (S) layer (A) ) is 15 ° C or lower, which is measured by the DSC method.

EMB 9. A multilayer article according to any one of the aforementioned EMB 1 to EMB 8, which comprises at least one tackifying resin in addition to the acrylate forming the layer.

EMB 10. The multilayer article according to any one of the aforementioned EMB 1 to EMB 9, which is foamed by using a microballoon.

EMB 11. The multilayer article of any one of the aforementioned EMB 1 to EMB 10, the foam carrier (S) layer having a layer thickness of 0.3 to 5 mm.

EMB 12. The multilayered article according to any one of the above EMB 1 to EMB 11, wherein the static glass transition temperature Tg (Kw1) of the discontinuous hydrocarbon phase Kw1 in the polymer composition (P) is in the range of -5 to +15 ° C Preferably, it is from 0 to +10 °C.

EMB 13. The multilayered article of any one of the above EMB 1 to EMB 12, wherein the static acrylate phase of the continuous acrylate phase in the polymer composition (P) has a static glass transition temperature Tg (Ac) of less than -10 ° C, preferably The range is -60 to -20 ° C, more preferably in the range of -50 to -30 ° C.

EMB 14. The multilayered article according to any one of the aforementioned EMB 1 to EMB 13, which has a number average molecular weight Mn of from 1,000 to 500,000 g/mole, which is measured by a GPC method, preferably from 2,000 to 30,000.

EMB 15. The multilayered article according to any one of the aforementioned EMB 1 to EMB 14, wherein the component of the comb copolymer (A) constitutes 30 to 64% by weight, preferably 45 to 60% by weight, to the polymer composition (P) The internal weight of the comb copolymer (A) and the at least one hydrocarbon component (B) is based on the total weight.

EMB 16. A multilayer article according to any one of the aforementioned EMB 1 to EMB 15, a macromonomer unit structure in the comb copolymer (A) It is 5-25% by weight, preferably 10-15% by weight, based on the total weight of the comb copolymer (A).

EMB 17. The multilayered article according to any one of the aforementioned EMB 1 to EMB 16, wherein the at least one (meth) acrylate monomer used to prepare the comb copolymer (A) comprises at least one selected from the group consisting of Group of monomers: acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, methyl acrylate, butyl acrylate, acrylic acid Ester, stearyl acrylate, isostearyl acrylate, amyl acrylate, isooctyl acrylate, decyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and 4-hydroxybutyl acrylate; preferably selected from In the group consisting of acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, methyl acrylate, butyl acrylate, acrylic acid Ester, stearyl acrylate, isostearyl acrylate, amyl acrylate, isooctyl acrylate and decyl acrylate.

EMB 18. The multilayer article according to any one of the aforementioned EMB 1 to EMB 17, wherein the polymerization of at least one (meth) acrylate monomer used to prepare the comb copolymer (A) is at least one further copolymerizable In the presence of a monomer, the at least one further copolymerizable single system is selected from the group consisting of itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, vinyl acetate, ethylene butyrate. Ester, vinyl propionate, vinyl isobutyrate, vinyl valerate, vinyl neodecanoate, N-vinylpyrrolidone and N-vinyl caprolactam.

EMB 19. The multilayered article according to any one of the aforementioned EMB 1 to EMB 18, wherein the comb copolymer (A) is polymerized to contain acrylic acid, butyl acrylate and 2-ethyl acrylate by the presence of at least one macromonomer. A co-monomer mixture of esters is obtained.

EMB 20. The multilayer article of any one of the aforementioned EMB 1 to EMB 19, wherein the polymerization of at least one (meth) acrylate monomer used to prepare the comb copolymer (A) is based on at least one further non-polyolefin macromolecule In the presence of a monomer, the further non-polyolefin macromonomer is preferably selected from the group consisting of polymethacrylates, polystyrenes, polydimethyloxanes, polyepoxys. Ethane and polypropylene oxide.

EMB 21. The multilayered article according to any one of the aforementioned EMB 1 to EMB 20, wherein the plasticizer resin of the hydrocarbon component (B) of the polymer composition (P) and the solid resin have a number average molecular weight Mn of 1000 g/mole or Less, this is measured by the GPC method.

EMB 22. The multilayered article of any one of the aforementioned EMB 1 to EMB 21, wherein the hydrocarbon component (B) of the polymer composition (P) is composed of a plasticizer resin and a solid resin.

EMB 23. The multilayered article of any one of the aforementioned EMB 1 to EMB 22, the polymer composition (P) further comprising a further hydrocarbon compound (C) having a number average molecular weight Mn of more than 1000 g/mole, which is by GPC The method measures, and the polymer composition preferably has a static glass transition temperature Tg(C) which is at the glass transition temperature Tg(Ac) of the continuous acrylate phase and the discontinuous hydrocarbon phase Tg (Kw1) )between.

EMB 24. The multilayered article according to any one of the aforementioned EMB 1 to EMB 23, the polymer composition (P) further comprising at least one plasticizer selected from the group consisting of an acrylate phase soluble in the comb copolymer, and an oil The additive of the group consisting of the resin is preferably a rosin ester and/or a terpene-phenol resin.

EMB 25. The multilayered article according to any one of the aforementioned EMB 1 to EMB 24, wherein the hydrocarbon component (B) of the polymer composition (P) and, if present, the total amount of the hydrocarbon compound (C) is 80% by weight or more More, based on the total component of the discontinuous hydrocarbon phase in the polymer composition (P).

EMB 26. The multilayered article according to any one of the aforementioned EMB 1 to EMB 25, which is a pressure-sensitive adhesive.

EMB 27. The multilayered article according to any one of the aforementioned EMB 1 to EMB 26, wherein the heterophasic polymer composition (P) applied to the foam carrier (S) layer has a weight per unit area of 40 to 100 g/square. The layer form of the meter is applied.

EMB 28. A method for producing a multilayer article according to any one of the aforementioned EMB 1 to EMB 27, the steps comprising: (i) providing a foam carrier (S) layer having an upper and a bottom acrylate substrate; (ii) applying a heterophasic polymer composition (P) to the upper and/or bottom edge of the foam carrier (S), the heterophasic polymer composition (P) comprising: ○ a comb copolymer (A), which may be carried out by at least one macromonomer selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butylene-propylene and isobutylene macromonomers Obtaining at least one (meth) acrylate monomer, and forming a continuous acrylate phase with a discontinuous hydrocarbon phase Kw; ○ and at least one hydrocarbon component (B), which is soluble in the comb a hydrocarbon phase Kw of the copolymer (A) and comprising at least one plasticizer resin and at least one solid resin; The heterophasic polymer composition (P) has a continuous acrylate phase having a static glass transition temperature Tg(Ac) as measured by the DSC method; and a discontinuous hydrocarbon phase Kw1 comprising the The hydrocarbon component (B) and having a static glass transition temperature Tg (Kw1), which is measured by the DSC method, wherein the Tg (Kw1) is 35 to 60 gram higher than the Tg (Ac), preferably 40 Up to 60 grams of ear, more preferably 45 to 60 grams of ear.

EMB 29. As in the method of EMB 28, the step (i) comprises the following method steps: (a) providing one or more acrylates and alkyl acrylates which can be polymerized by free-type or controlled-type radical polymerization; (b) polymerization in a method The acrylate and alkyl acrylate provided in step (a) to form a polyacrylate; (c) converting the produced polyacrylate into a polyacrylate foam; and (d) the polyacrylate The foamed material is molded into a foamed carrier (S) layer.

EMB 30. An adhesive tape comprising a multilayer article such as any one of EMB 1 to EMB 27.

EMB 31. A use of a multilayer article such as any one of EMB 1 to EMB 27 for use in gluing and bonding of articles.

1‧‧‧First assembly

2‧‧‧Second assembly

3‧‧‧ third assembly

4‧‧‧ polishing roller

5‧‧‧Mold

11‧‧‧Connected section

11‧‧‧heatable hose

22,23,34,35,36‧‧‧measuring points

24‧‧‧Second connection

31,32‧‧‧ mixed area

33,34,35‧‧‧Measuring equipment

36‧‧‧Sliding seal ring

37‧‧‧Transportation unit

41,42,43‧‧‧roll

44‧‧‧Carrier materials

Section S‧‧‧

V‧‧‧vacuum dome

Claims (17)

A multilayer article comprising: - a foam carrier support (S) of at least one acrylate substrate; and - a heterophasic polymer composition (P) applied to the layer; the heterophasic polymer composition (P) comprising : ○ a comb-shaped copolymer (A) which can be obtained by at least one selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butylene-propylene and isobutylene macromonomers. In the presence of a macromonomer, polymerizing at least one (meth) acrylate monomer, and forming a continuous acrylate phase with a discontinuous hydrocarbon phase Kw; ○ and at least one hydrocarbon component (B), Is soluble in the hydrocarbon phase Kw of the comb copolymer (A) and comprises at least one plasticizer resin and at least one solid resin; the heterophasic polymer composition (P) has a continuous acrylate phase, Having a static glass transition temperature Tg(Ac), as measured by the DSC method; and a discontinuous hydrocarbon phase Kw1 comprising the hydrocarbon component (B) and having a static glass transition temperature Tg (Kw1), It is measured by the DSC method, in which Tg (Kw1) is 35 to 60 gram (K) higher than Tg (Ac). The multi-layered article of claim 1, the foamed carrier (S) of the acrylate substrate is a viscoelastic foam carrier. The multilayer article according to any one of the preceding claims, wherein the acrylate-forming polyacrylate of the foam carrier (S) layer is polymerizable by free or controlled free radical polymerization of one or more acrylates and Obtained with an alkyl acrylate. The multilayer article according to any one of the preceding claims, wherein the acrylate forming the foam carrier (S) layer is a crosslinked polyacrylate, preferably a thermally crosslinked polyacrylate. The multilayer article according to any one of the preceding claims, wherein the acrylate which forms the foam carrier (S) layer is a polyacrylate which can be polymerized by the following groups (a1) to (a3) The monomer consisting of the body obtains: (a1) 70 to 100% by weight of the acrylate and/or methacrylate and/or free acid according to formula (I): Wherein R ¹ is H or CH ₃ ; and R ² represents H or C ₁ -C ₁₄ alkyl; (a2) 0 to 30% by weight of an olefinically unsaturated monomer which is copolymerizable with the monomer of group (a1) Polymerized and having at least one functional group; and (a3) optionally further acrylate and/or methacrylate and/or olefinically unsaturated monomer, preferably in a component of from 0 to 5% by weight, which is compatible with the group (a1) The monomer is copolymerized and has at least one functional group that causes covalent crosslinking by a coupling agent. The multilayer system of claim 5, wherein the single system of the group (a1) is selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, and propyl methacrylate. , n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-decyl acrylate, lauryl acrylate, stearic acid acrylate Esters, stearyl methacrylate, acrylate and their branched isomers such as, for example, 2-ethylhexyl acrylate, and also mixtures thereof; And/or the single system of the group (a2) is selected from the group consisting of maleic anhydride, itaconic anhydride, glycidyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate , butyl phenyl acrylate, butyl phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-butyl acrylate Oxyethyl ester, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate and tetrahydrofurfuryl acrylate And/or a mixture thereof; and/or the single system of the group (a3) is selected from the group consisting of hydroxyethyl acrylate, 3-hydroxypropyl acrylate, hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl alcohol, itaconic acid, acrylamide and cyanoethyl methacrylate, cyanoethyl acrylate, 6-hydroxyhexyl methacrylate, N - Tert-butyl butyl acrylamide, N-methylol methacrylamide, N-(butoxymethyl)methacrylamide, N-methylol decylamine , N-(ethoxymethyl) acrylamide, N-isopropyl acrylamide, vinyl acetate, β-propylene methoxy propionic acid, trichloroacrylic acid, fumaric acid, crotonic acid, aconite Acid, dimethacrylic acid and 4-vinylbenzoic acid, and also mixtures thereof. A multilayer article according to any of the preceding claims, wherein the multilayer article is a tape; and/or the foam carrier (S) layer is foamed by using a microballoon. A multilayer article according to any of the preceding claims, wherein the static glass transition temperature Tg (Kw1) of the discontinuous hydrocarbon phase in the polymer composition (P) is in the range of -5 to +15 ° C, Good for 0 to +10 ° C; and / or the static acrylate phase of the polymer composition (P) has a static glass transition temperature Tg (Ac) of less than -10 ° C, preferably in the range of -60 to -20 ° C, more preferably In the range of -50 to -30 °C. The multilayered article according to any one of the preceding claims, wherein the component of the comb copolymer (A) constitutes 30 to 64% by weight, preferably 45 to 60% by weight, to be in the polymer composition (P). The comb copolymer (A) is based on the total weight of the at least one hydrocarbon component (B); and/or the macromonomer unit in the comb copolymer (A) constitutes 5-25% by weight, It is preferably 10 to 15% by weight based on the total weight of the comb copolymer (A). The multilayer article according to any one of the preceding claims, wherein the at least one (meth) acrylate monomer which can be used to prepare the comb copolymer (A) comprises at least one selected from the group consisting of Body: acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, methyl acrylate, butyl acrylate, acrylic acid Ester, stearyl acrylate, isostearyl acrylate, amyl acrylate, isooctyl acrylate, decyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and 4-hydroxybutyl acrylate; preferably selected from The following group: acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, methyl acrylate, butyl acrylate, acrylic acid Ester, stearyl acrylate, isostearyl acrylate, amyl acrylate, isooctyl acrylate and decyl acrylate. The multilayer article according to any of the preceding claims, wherein the polymerization of at least one (meth) acrylate monomer used to prepare the comb copolymer (A) is in the presence of at least one further copolymerizable monomer Performing at least one further system which is further copolymerizable is selected from the following Group of components: itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl isobutyrate, vinyl valerate, vinyl neodecanoate Vinyl versatates, N-vinylpyrrolidone and N-vinyl caprolactam. The multilayered article according to any one of the preceding claims, wherein the plasticizer resin of the hydrocarbon component (B) and the solid resin have a number average molecular weight Mn of 1000 g/mole or less, by GPC Method measurement. The multilayer composition of claim 12, the polymer composition (P) further comprising a further hydrocarbon compound (C) having a number average molecular weight Mn of more than 1000 g/mole, as measured by a GPC method, and the polymerization Preferably, the composition has a static glass transition temperature Tg (C) between the glass transition temperature Tg (Ac) of the continuous acrylate phase and the discontinuous hydrocarbon phase Tg (Kw1). A multilayer article according to any one of the preceding claims, wherein the polymer composition (P) is a pressure sensitive adhesive; and/or the heterophasic polymer is applied to the foam carrier (S) layer. The substance (P) is applied in the form of a layer having a weight per unit area of 40 to 100 g/m 2 . A method for producing a multilayer article according to any of the preceding claims, comprising the steps of: (i) providing a foam carrier (S) having an upper and a bottom acrylate substrate; and (ii) A heterophasic polymer composition (P) is applied to the upper side and/or the bottom side of the foam carrier (S), the heterophasic polymer composition (P) comprising: ○ a comb-shaped copolymer (A) which can be obtained by at least one group selected from the group consisting of polymerizable ethylene-butene, ethylene-propylene, ethylene-butylene-propylene and isobutylene macromonomers In the presence of a molecular monomer, polymerizing at least one (meth) acrylate monomer, and forming a continuous acrylate phase with a discontinuous hydrocarbon phase Kw; ○ and at least one hydrocarbon component (B), Is soluble in the hydrocarbon phase Kw of the comb copolymer (A) and comprises a plasticizer resin and a solid resin; the heterophasic polymer composition (P) has a continuous acrylate phase having a static Glass transition temperature Tg(Ac), as measured by the DSC method; and a discontinuous hydrocarbon phase Kw1 comprising the hydrocarbon component (B) and having a static glass transition temperature Tg (Kw1) by The DSC method measures that Tg (Kw1) is 35 to 60 gram (K) higher than Tg (Ac). An adhesive tape comprising a multilayer article according to any one of claims 1 to 14. A use of a multilayer article according to any one of claims 1 to 14 for use in gluing and bonding of articles.